Hydroformylation processes

ABSTRACT

This invention relates to a process for separating one or more phosphorus acidic compounds from a hydroformylation reaction product fluid containing said one or more phosphorus acidic compounds, a metal-organophosphite ligand complex catalyst and optionally free organophosphite ligand which process comprises (a) treating said hydroformylation reaction product fluid with water sufficient to remove at least some amount of said one or more phosphorus acidic compounds from said hydroformylation reaction product fluid and (b) treating the water which contains phosphorus acidic compounds removed from said hydroformylation reaction product fluid with an ion exchange resin sufficient to remove at least some amount of said one or more phosphorus acidic compounds from said water.

This application claims the benefit of provisional U.S. patentapplication Ser. Nos. 60/008289, 60/008763, 60/008284 and 60/008286, allfiled Dec. 6, 1995, and all of which are incorporated herein byreference.

BRIEF SUMMARY OF THE INVENTION

1. Technical Field

This invention relates to an improved metal-organophosphite ligandcomplex catalyzed hydroformylation process directed to producingaldehydes. More particularly, this invention relates to the use of oneor more water scrubbers in conjunction with one or more ion exchangeresins in metal-organophosphite ligand complex catalyzedhydroformylation processes to prevent and/or lessen hydrolyticdegradation of the organophosphite ligand and deactivation of themetal-organophosphite ligand complex catalyst of such hydroformylationprocesses.

2. Background of the Invention

It is well known in the art that aldehydes may be readily produced byreacting an olefinically unsaturated compound with carbon monoxide andhydrogen in the presence of a rhodium-organophosphite ligand complexcatalyst and that preferred processes involve continuoushydroformylation and recycling of the catalyst solution such asdisclosed, for example, in U.S. Pat. Nos. 4,148,830; 4,717,775 and4,769,498. Such aldehydes have a wide range of known utility and areuseful, for example, as intermediates for hydrogenation to aliphaticalcohols, for aldol condensation to produce plasticizers, and foroxidation to produce aliphatic acids.

However, notwithstanding the benefits attendant with suchrhodium-organophosphite ligand complex catalyzed liquid recyclehydroformylation processes, stabilization of the catalyst andorganophosphite ligand remains a primary concern of the art. Obviouslycatalyst stability is a key issue in the employment of any catalyst.Loss of catalyst or catalytic activity due to undesirable reactions ofthe highly expensive rhodium catalysts can be detrimental to theproduction of the desired aldehyde. Likewise degradation of theorganophosphite ligand employed during the hydroformylation process canlead to poisoning organophosphite compounds or inhibitors or acidicbyproducts that can lower the catalytic activity of the rhodiumcatalyst. Moreover, production costs of the aldehyde product obviouslyincrease when productivity of the catalyst decreases.

Numerous methods have been proposed to maintain catalyst and/ororganophosphite ligand stability. For instance, U.S. Pat. No. 5,288,918suggests employing a catalytic activity enhancing additive such as waterand/or a weakly acidic compound; U.S. Pat. No. 5,364,950 suggests addingan epoxide to stabilize the organophosphite ligand; and U.S. Pat. No.4,774,361 suggests carrying out the vaporization separation employed torecover the aldehyde product from the catalyst in the presence of anorganic polymer containing polar functional groups selected from theclass consisting of amide, ketone, carbamate, urea, and carbonateradicals in order to prevent and/or lessen rhodium precipitation fromsolution as rhodium metal or in the form of clusters of rhodium.Notwithstanding the value of the teachings of said references, thesearch for alternative methods and hopefully an even better and moreefficient means for stabilizing the rhodium catalyst and organophosphiteligand employed remains an ongoing activity in the art.

For instance, a major cause of organophosphite ligand degradation andcatalyst deactivation of rhodium-organophosphite ligand complexcatalyzed hydroformylation processes is due to the hydrolyticinstability of the organophosphite ligands. All organophosphites aresusceptible to hydrolysis in one degree or another, the rate ofhydrolysis of organophosphites in general being dependent on thestereochemical nature of the organophosphite. In general, the bulkierthe steric environment around the phosphorus atom, the slower thehydrolysis rate. For example, tertiary triorganophosphites such astriphenylphosphite are more susceptible to hydrolysis thandiorganophosphites, such as disclosed in U.S. Pat. No. 4,737,588, andorganopolyphosphites such as disclosed in U.S. Pat. Nos. 4,748,261 and4,769,498. Moreover, all such hydrolysis reactions invariably producephosphorus acidic compounds which catalyze the hydrolysis reactions. Forexample, the hydrolysis of a tertiary organophosphite produces aphosphonic acid diester, which is hydrolyzable to a phosphonic acidmonoester, which in turn is hydrolyzable to H₃ PO₃ acid. Moreover,hydrolysis of the ancillary products of side reactions, such as betweena phosphonic acid diester and the aldehyde or between certainorganophosphite ligands and an aldehyde, can lead to production ofundesirable strong aldehyde acids, e.g., n-C₃ H₇ CH(OH)P(O)(OH)₂.

Indeed even highly desirable sterically-hindered organobisphosphiteswhich are not very hydrolyzable can react with the aldehyde product toform poisoning organophosphites, e.g., organomonophosphites, which arenot only catalytic inhibitors, but far more susceptible to hydrolysisand the formation of such aldehyde acid byproducts, e.g., hydroxy alkylphosphonic acids, as shown, for example, in U.S. Pat. Nos. 5,288,918 and5,364,950. Further, the hydrolysis of organophosphite ligands may beconsidered as being autocatalytic in view of the production of suchphosphorus acidic compounds, e.g., H₃ PO₃, aldehyde acids such ashydroxy alkyl phosphonic acids, H₃ PO₄ and the like, and if leftunchecked the catalyst system of the continuous liquid recyclehydroformylation process will become more and more acidic in time. Thusin time the eventual build-up of an unacceptable amount of suchphosphorus acidic materials can cause the total destruction of theorganophosphite present, thereby rendering the hydroformylation catalysttotally ineffective (deactivated) and the valuable rhodium metalsusceptible to loss, e.g., due to precipitation and/or depositing on thewalls of the reactor.

A method that has been proposed for removing phosphorus acidic compoundsfrom a hydroformylation system involves passing a hydroformylationprocess stream directly through an anion exchange resin bed. However,under hydroformylation conditions, rhodium precipitation can occur onthe resin surface and pores, thereby causing process complications.

Accordingly, a successful method for preventing and/or lessening suchhydrolytic degradation of the organophosphite ligand and deactivation ofthe catalyst would be highly desirable to the art.

DISCLOSURE OF THE INVENTION

It has now been discovered that one or more water scrubbers inconjunction with one or more ion exchange resins may be employed toeffectively remove such phosphorus acidic compounds and thus preventand/or lessen hydrolytic degradation of organophosphite ligands anddeactivation of metal-organophosphite ligand complex catalysts that mayoccur over the course of time during a hydroformylation process directedto producing aldehydes. It has been discovered that ion exchange resinscan be used to improve stability of metal-organophosphite ligand complexcatalyzed hydroformylation processes through the use of an intermediateagent, i.e., water, which acts to transfer acidity from thehydroformylation reaction product fluid to the ion exchange resin. Ithas also been surprisingly discovered that minimum loss oforganophosphite ligand occurs when a hydroformylation reaction productfluid containing a metal-organophosphite ligand complex catalyst iscontacted with water and the contacted water thereafter treated with theion exchange resins even at elevated temperatures.

This invention relates in part to a process for separating one or morephosphorus acidic compounds from a hydroformylation reaction productfluid containing said one or more phosphorus acidic compounds, ametal-organophosphite ligand complex catalyst and optionally freeorganophosphite ligand which process comprises (a) treating saidhydroformylation reaction product fluid with water sufficient to removeat least some amount of said one or more phosphorus acidic compoundsfrom said hydroformylation reaction product fluid and (b) treating thewater which contains phosphorus acidic compounds removed from saidhydroformylation reaction product fluid with an ion exchange resinsufficient to remove at least some amount of said one or more phosphorusacidic compounds from said water.

This invention also relates in part to a process for stabilizing anorganophosphite ligand against hydrolytic degradation and/or ametal-organophosphite ligand complex catalyst against deactivation whichprocess comprises (a) treating a hydroformylation reaction product fluidcontaining a metal-organophosphite ligand complex catalyst andoptionally free organophosphite ligand and which also contains one ormore phosphorus acidic compounds, with water sufficient to remove atleast some amount of said one or more phosphorus acidic compounds fromsaid hydroformylation reaction product fluid and (b) treating the waterwhich contains phosphorus acidic compounds removed from saidhydroformylation reaction product fluid with an ion exchange resinsufficient to remove at least some amount of said one or more phosphorusacidic compounds from said water.

This invention further relates in part to a process for preventingand/or lessening hydrolytic degradation of an organophosphite ligandand/or deactivation of a metal-organophosphite ligand complex catalystwhich process comprises (a) treating a hydroformylation reaction productfluid containing a metal-organophosphite ligand complex catalyst andoptionally free organophosphite ligand and which also contains one ormore phosphorus acidic compounds, with water sufficient to remove atleast some amount of said one or more phosphorus acidic compounds fromsaid hydroformylation reaction product fluid and (b) treating the waterwhich contains phosphorus acidic compounds removed from saidhydroformylation reaction product fluid with an ion exchange resinsufficient to remove at least some amount of said one or more phosphorusacidic compounds from said water.

This invention yet further relates in part to an improvedhydroformylation process for producing one or more aldehydes whichcomprises (i) reacting in at least one reaction zone one or moreolefinic unsaturated compounds with carbon monoxide and hydrogen in thepresence of a metal-organophosphite ligand complex catalyst andoptionally free organophosphite ligand to produce a reaction productfluid comprising one or more aldehydes and (ii) separating in at leastone separation zone or in said at least one reaction zone the one ormore aldehydes from said reaction product fluid, the improvementcomprising preventing and/or lessening hydrolytic degradation of anysaid organophosphite ligand and deactivation of saidmetal-organophosphite ligand complex catalyst by (a) treating in atleast one scrubber zone at least a portion of said reaction productfluid derived from said hydroformylation process and which also containsphosphorus acidic compounds formed during said hydroformylation processwith water sufficient to remove at least some amount of the phosphorusacidic compounds from said reaction product fluid and (b) treating in atleast one ion exchange zone at least a portion of the water whichcontains phosphorus acidic compounds removed from said reaction productfluid with one or more ion exchange resins sufficient to remove at leastsome amount of the phosphorus acidic compounds from said water.

This invention also relates in part to an improved hydroformylationprocess for producing one or more aldehydes which comprises (i) reactingin at least one reaction zone one or more olefinic unsaturated compoundswith carbon monoxide and hydrogen in the presence of ametal-organophosphite ligand complex catalyst and optionally freeorganophosphite ligand to produce a reaction product fluid comprisingone or more aldehydes and (ii) separating in at least one separationzone or in said at least one reaction zone the one or more aldehydesfrom said reaction product fluid, the improvement comprising preventingand/or lessening hydrolytic degradation of any said organophosphiteligand and deactivation of said metal-organophosphite ligand complexcatalyst by (a) treating in at least one scrubber zone at least aportion of said reaction product fluid derived from saidhydroformylation process and which also contains phosphorus acidiccompounds formed during said hydroformylation process with watersufficient to remove at least some amount of the phosphorus acidiccompounds from said reaction product fluid, (b) returning the treatedreaction product fluid to said at least one reaction zone or said atleast one separation zone, (c) treating in at least one ion exchangezone at least a portion of the water which contains phosphorus acidiccompounds removed from said reaction product fluid with one or more ionexchange resins sufficient to remove at least some amount of thephosphorus acidic compounds from said water, and (d) returning thetreated water to said at least one scrubber zone.

This invention further relates in part to an improved hydroformylationprocess for producing aldehydes which comprises (i) reacting in at leastone reaction zone one or more olefinic unsaturated compounds with carbonmonoxide and hydrogen in the presence of a metal-organophosphite ligandcomplex catalyst and optionally free organophosphite ligand to produce areaction product fluid comprising one or more aldehydes and (ii)separating in at least one separation zone or in said at least onereaction zone the one or more aldehydes from said reaction productfluid, the improvement comprising preventing and/or lessening hydrolyticdegradation of any said organophosphite ligand and deactivation of saidmetal-organophosphite ligand complex catalyst by (a) withdrawing fromsaid at least one reaction zone or said at least one separation zone atleast a portion of a reaction product fluid derived from saidhydroformylation process and which also contains phosphorus acidiccompounds formed during said hydroformylation process, (b) treating inat least one scrubber zone at least a portion of the withdrawn reactionproduct fluid derived from said hydroformylation process and which alsocontains phosphorus acidic compounds formed during said hydroformylationprocess with water sufficient to remove at least some amount of thephosphorus acidic compounds from said reaction product fluid, (c)returning the treated reaction product fluid to said at least onereaction zone or said at least one separation zone, (d) withdrawing fromsaid at least one scrubber zone at least a portion of said water whichcontains phosphorus acidic compounds removed from said reaction productfluid, (e) treating in at least one ion exchange zone at least a portionof the withdrawn water which contains phosphorus acidic compoundsremoved from said reaction product fluid with one or more ion exchangeresins sufficient to remove at least some amount of the phosphorusacidic compounds from said water, (f) returning the treated water tosaid at least one scrubber zone, and (g) optionally regenerating saidone or more ion exchange resins.

This invention yet further relates in part to an improvedhydroformylation process for producing one or more aldehydes whichcomprises (i) reacting in at least one reaction zone one or moreolefinic unsaturated compounds with carbon monoxide and hydrogen in thepresence of a metal-organophosphite ligand complex catalyst andoptionally free organophosphite ligand to produce a reaction productfluid comprising one or more aldehydes and (ii) separating in at leastone separation zone or in said at least one reaction zone the one ormore aldehydes from said reaction product fluid, the improvementcomprising preventing and/or lessening hydrolytic degradation of anysaid organophosphite ligand and deactivation of saidmetal-organophosphite ligand complex catalyst by (a) treating at least aportion of said reaction product fluid derived from saidhydroformylation process and which also contains phosphorus acidiccompounds formed during said hydroformylation process by introducingwater into said at least one reaction zone and/or said at least oneseparation zone sufficient to remove at least some amount of thephosphorus acidic compounds from said reaction product fluid and (b)treating in at least one ion exchange zone at least a portion of thewater which contains phosphorus acidic compounds removed from saidreaction product fluid with one or more ion exchange resins sufficientto remove at least some amount of the phosphorus acidic compounds fromsaid water.

This invention also relates in part to an improved hydroformylationprocess for producing aldehydes which comprises (i) reacting in at leastone reaction zone one or more olefinic unsaturated compounds with carbonmonoxide and hydrogen in the presence of a metal-organophosphite ligandcomplex catalyst and optionally free organophosphite ligand to produce areaction product fluid comprising one or more aldehydes and (ii)separating in at least one separation zone or in said at least onereaction zone the one or more aldehydes from said reaction productfluid, the improvement comprising preventing and/or lessening hydrolyticdegradation of any said organophosphite ligand and deactivation of saidmetal-organophosphite ligand complex catalyst by (a) withdrawing fromsaid at least one reaction zone or said at least one separation zone atleast a portion of a reaction product fluid derived from saidhydroformylation process and which also contains phosphorus acidiccompounds formed during said hydroformylation process, (b) treating inat least one scrubber zone at least a portion of the withdrawn reactionproduct fluid derived from said hydroformylation process and which alsocontains phosphorus acidic compounds formed during said hydroformylationprocess with water sufficient to remove at least some amount of thephosphorus acidic compounds from said reaction product fluid, (c)returning the treated reaction product fluid to said at least onereaction zone or said at least one separation zone, (d) treating in saidat least one scrubber zone at least a portion of the withdrawn waterwhich contains phosphorus acidic compounds removed from said reactionproduct fluid with one or more ion exchange resins sufficient to removeat least some amount of the phosphorus acidic compounds from said water,and (e) optionally regenerating said one or more ion exchange resins.

This invention further relates in part to an improved hydroformylationprocess for producing aldehydes which comprises (i) reacting in at leastone reaction zone one or more olefinic unsaturated compounds with carbonmonoxide and hydrogen in the presence of a metal-organophosphite ligandcomplex catalyst and optionally free organophosphite ligand to produce areaction product fluid comprising one or more aldehydes and (ii)separating in at least one separation zone or in said at least onereaction zone the one or more aldehydes from said reaction productfluid, the improvement comprising preventing and/or lessening hydrolyticdegradation of any said organophosphite ligand and deactivation of saidmetal-organophosphite ligand complex catalyst by (a) withdrawing fromsaid at least one reaction zone or said at least one separation zone atleast a portion of a reaction product fluid derived from saidhydroformylation process and which also contains phosphorus acidiccompounds formed during said hydroformylation process, (b) treating inat least one scrubber zone at least a portion of the withdrawn reactionproduct fluid derived from said hydroformylation process and which alsocontains phosphorus acidic compounds formed during said hydroformylationprocess with water sufficient to remove at least some amount of thephosphorus acidic compounds from said reaction product fluid, (c)returning the treated reaction product fluid to said at least onereaction zone or said at least one separation zone, (d) treating in saidat least one scrubber zone at least a portion of the withdrawn waterwhich contains phosphorus acidic compounds removed from said reactionproduct fluid with one or more amines sufficient to remove at least someamount of the phosphorus acidic compounds from said water, and (e)optionally replacing said one or more amines.

This invention yet further relates in part to an improvedhydroformylation process for producing one or more aldehydes whichcomprises (i) reacting in at least one reaction zone one or moreolefinic unsaturated compounds with carbon monoxide and hydrogen in thepresence of a metal-organophosphite ligand complex catalyst andoptionally free organophosphite ligand to produce a reaction productfluid comprising one or more aldehydes and (ii) separating in at leastone separation zone or in said at least one reaction zone the one ormore aldehydes from said reaction product fluid, the improvementcomprising preventing and/or lessening hydrolytic degradation of anysaid organophosphite ligand and deactivation of saidmetal-organophosphite ligand complex catalyst by treating at least aportion of said reaction product fluid derived from saidhydroformylation process and which also contains phosphorus acidiccompounds formed during said hydroformylation process by introducing oneor more amines into said at least one reaction zone and/or said at leastone separation zone sufficient to remove at least some amount of thephosphorus acidic compounds from said reaction product fluid.

This invention also relates in part to an improved hydroformylationprocess for producing one or more aldehydes which comprises (i) reactingin at least one reaction zone one or more olefinic unsaturated compoundswith carbon monoxide and hydrogen in the presence of ametal-organophosphite ligand complex catalyst and optionally freeorganophosphite ligand to produce a reaction product fluid comprisingone or more aldehydes and (ii) separating in at least one separationzone or in said at least one reaction zone the one or more aldehydesfrom said reaction product fluid, the improvement comprising preventingand/or lessening hydrolytic degradation of any said organophosphiteligand and deactivation of said metal-organophosphite ligand complexcatalyst by treating at least a portion of said reaction product fluidderived from said hydroformylation process and which also containsphosphorus acidic compounds formed during said hydroformylation processby introducing one or more phosphines into said at least one reactionzone and/or said at least one separation zone sufficient to remove atleast some amount of the phosphorus acidic compounds from said reactionproduct fluid.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a simplified process flow diagram of a process for recoveringand returning one or more aldehydes removed by water extraction to thehydroformylation process in accordance with this invention.

DETAILED DESCRIPTION

The hydroformylation processes of this invention may be asymmetric ornon-asymmetric, the preferred processes being non-asymmetric, and may beconducted in any continuous or semi-continuous fashion and may involveany catalyst liquid and/or gas recycle operation desired. Thus it shouldbe clear that the particular hydroformylation process for producing suchaldehydes from an olefinic unsaturated compound, as well as the reactionconditions and ingredients of the hydroformylation process are notcritical features of this invention. As used herein, the term"hydroformylation" is contemplated to include, but not limited to, allpermissible asymmetric and non-asymmetric hydroformylation processeswhich involve converting one or more substituted or unsubstitutedolefinic compounds or a reaction mixture comprising one or moresubstituted or unsubstituted olefinic compounds to one or moresubstituted or unsubstituted aldehydes or a reaction mixture comprisingone or more substituted or unsubstituted aldehydes. As used herein, theterm "reaction product fluid" is contemplated to include, but notlimited to, a reaction mixture containing an amount of any one or moreof the following: (a) a metal-organophosphite ligand complex catalyst,(b) free organophosphite ligand, (c) one or more phosphorus acidiccompounds formed in the reaction, (d) aldehyde product formed in thereaction, (e) unreacted reactants, and (f) an organic solubilizing agentfor said metal-organophosphite ligand complex catalyst and said freeorganophosphite ligand. The reaction product fluid encompasses, but isnot limited to, (a) the reaction medium in the reaction zone, (b) thereaction medium stream on its way to the separation zone, (c) thereaction medium in the separation zone, (d) the recycle stream betweenthe separation zone and the reaction zone, (e) the reaction mediumwithdrawn from the reaction zone or separation zone for treatment withthe water, (f) the withdrawn reaction medium treated with the water, (g)the treated reaction medium returned to the reaction zone or separationzone, and (h) reaction medium in external cooler.

Illustrative metal-organophosphite ligand complex catalyzedhydroformylation processes which may experience such hydrolyticdegradation of the organophosphite ligand and catalytic deactivationinclude such processes as described, for example, in U.S. Pat. Nos.4,148,830; 4,593,127; 4,769,498; 4,717,775; 4,774,361; 4,885,401;5,264,616; 5,288,918; 5,360,938; 5,364,950; and 5,491,266; thedisclosures of which are incorporated herein by reference. Accordingly,the hydroformylation processing techniques of this invention maycorrespond to any known processing techniques. Preferred processes arethose involving catalyst liquid recycle hydroformylation processes.

In general, such catalyst liquid recycle hydroformylation processesinvolve the production of aldehydes by reacting an olefinic unsaturatedcompound with carbon monoxide and hydrogen in the presence of ametal-organophosphite ligand complex catalyst in a liquid medium thatalso contains an organic solvent for the catalyst and ligand. Preferablyfree organophosphite ligand is also present in the liquidhydroformylation reaction medium. By "free organophosphite ligand" ismeant organophosphite ligand that is not complexed with (tied to orbound to) the metal, e.g., metal atom, of the complex catalyst. Therecycle procedure generally involves withdrawing a portion of the liquidreaction medium containing the catalyst and aldehyde product from thehydroformylation reactor (i.e., reaction zone), either continuously orintermittently, and recovering the aldehyde product therefrom by use ofa composite membrane such as disclosed in U.S. Pat. No. 5,430,194 andcopending U.S. patent application Ser. No. 08/430,790, filed May 5,1995, the disclosures of which are incorporated herein by reference, orby the more conventional and preferred method of distilling it (i.e.,vaporization separation) in one or more stages under normal, reduced orelevated pressure, as appropriate, in a separate distillation zone, thenon-volatilized metal catalyst containing residue being recycled to thereaction zone as disclosed, for example, in U.S. Pat. No. 5,288,918.Condensation of the volatilized materials, and separation and furtherrecovery thereof, e.g., by further distillation, can be carried out inany conventional manner, the crude aldehyde product can be passed on forfurther purification and isomer separation, if desired, and anyrecovered reactants, e.g., olefinic starting material and syn gas, canbe recycled in any desired manner to the hydroformylation zone(reactor). The recovered metal catalyst containing raffinate of suchmembrane separation or recovered non-volatilized metal catalystcontaining residue of such vaporization separation can be recycled, tothe hydroformylation zone (reactor) in any conventional manner desired.

In a preferred embodiment, the hydroformylation reaction product fluidsemployable herein includes any fluid derived from any correspondinghydroformylation process that contains at least some amount of fourdifferent main ingredients or components, i.e., the aldehyde product, ametal-organophosphite ligand complex catalyst, free organophosphiteligand and an organic solubilizing agent for said catalyst and said freeligand, said ingredients corresponding to those employed and/or producedby the hydroformylation process from whence the hydroformylationreaction mixture starting material may be derived. It is to beunderstood that the hydroformylation reaction mixture compositionsemployable herein can and normally will contain minor amounts ofadditional ingredients such as those which have either been deliberatelyemployed in the hydroformylation process or formed in situ during saidprocess. Examples of such ingredients that can also be present includeunreacted olefin starting material, carbon monoxide and hydrogen gases,and in situ formed type products, such as saturated hydrocarbons and/orunreacted isomerized olefins corresponding to the olefin startingmaterials, and high boiling liquid aldehyde condensation byproducts, aswell as other inert co-solvent type materials or hydrocarbon additives,if employed.

Illustrative metal-organophosphite ligand complex catalysts employablein such hydroformylation reactions encompassed by this invention as wellas methods for their preparation are well known in the art and includethose disclosed in the above mentioned patents. In general suchcatalysts may be preformed or formed in situ as described in suchreferences and consist essentially of metal in complex combination withan organophosphite ligand. It is believed that carbon monoxide is alsopresent and complexed with the metal in the active species. The activespecies may also contain hydrogen directly bonded to the metal.

The catalyst useful in the hydroformylation process includes ametal-organophosphite ligand complex catalyst which can be opticallyactive or non-optically active. The permissible metals which make up themetal-organophosphite ligand complexes include Group 8, 9 and 10 metalsselected from rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru),iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt), osmium (Os) andmixtures thereof, with the preferred metals being rhodium, cobalt,iridium and ruthenium, more preferably rhodium, cobalt and ruthenium,especially rhodium. Mixtures of metals from Groups 8, 9 and 10 may alsobe used in this invention. The permissible organophosphite ligands whichmake up the metal-organophosphite ligand complexes and freeorganophosphite ligand include mono-, di-, tri- and higherpolyorganophosphites. Mixtures of such ligands may be employed ifdesired in the metal-organophosphite ligand complex catalyst and/or freeligand and such mixtures may be the same or different. This invention isnot intended to be limited in any manner by the permissibleorganophosphite ligands or mixtures thereof. It is to be noted that thesuccessful practice of this invention does not depend and is notpredicated on the exact structure of the metal-organophosphite ligandcomplex species, which may be present in their mononuclear, dinuclearand/or higher nuclearity forms. Indeed, the exact structure is notknown. Although it is not intended herein to be bound to any theory ormechanistic discourse, it appears that the catalytic species may in itssimplest form consist essentially of the metal in complex combinationwith the organophosphite ligand and carbon monoxide and/or hydrogen whenused.

The term "complex" as used herein and in the claims means a coordinationcompound formed by the union of one or more electronically richmolecules or atoms capable of independent existence with one or moreelectronically poor molecules or atoms, each of which is also capable ofindependent existence. For example, the organophosphite ligandsemployable herein may possess one or more phosphorus donor atoms, eachhaving one available or unshared pair of electrons which are eachcapable of forming a coordinate covalent bond independently or possiblyin concert (e.g., via chelation) with the metal. Carbon monoxide (whichis also properly classified as a ligand) can also be present andcomplexed with the metal. The ultimate composition of the complexcatalyst may also contain an additional ligand, e.g., hydrogen or ananion satisfying the coordination sites or nuclear charge of the metal.Illustrative additional ligands include, for example, halogen (Cl, Br,I), alkyl, aryl, substituted aryl, acyl, CF₃, C₂ F₅, CN, (R)₂ PO andRP(O)(OH)O (wherein each R is the same or different and is a substitutedor unsubstituted hydrocarbon radical, e.g., the alkyl or aryl), acetate,acetylacetonate, SO₄, PF₄, PF₆, NO₂, NO₃, CH₃ O, CH₂ ═CHCH₂, CH₃CH═CHCH₂, C₆ H₅ CN, CH₃ CN, NH₃, pyridine, (C₂ H₅)₃ N, mono-olefins,diolefins and triolefins, tetrahydrofuran, and the like. It is of courseto be understood that the complex species are preferably free of anyadditional organic ligand or anion that might poison the catalyst orhave an undue adverse effect on catalyst performance. It is preferred inthe metal-organophosphite ligand complex catalyzed hydroformylationreactions that the active catalysts be free of halogen and sulfurdirectly bonded to the metal, although such may not be absolutelynecessary.

The number of available coordination sites on such metals is well knownin the art. Thus the catalytic species may comprise a complex catalystmixture, in their monomeric, dimeric or higher nuclearity forms, whichare preferably characterized by at least one organophosphite-containingmolecule complexed per one molecule of metal, e.g., rhodium. Forinstance, it is considered that the catalytic species of the preferredcatalyst employed in a hydroformylation reaction may be complexed withcarbon monoxide and hydrogen in addition to the organophosphite ligandsin view of the carbon monoxide and hydrogen gas employed by thehydroformylation reaction.

The organophosphites that may serve as the ligand of themetal-organophosphite ligand complex catalyst and/or free ligand of thehydroformylation processes and reaction product fluids of this inventionmay be of the achiral (optically inactive) or chiral (optically active)type and are well known in the art. Achiral organophosphites arepreferred.

Among the organophosphites that may serve as the ligand of themetal-organophosphite ligand complex catalyst containing reactionproduct fluids of this invention and/or any free organophosphite ligandof the hydroformylation process that might also be present in saidreaction product fluids are monoorganophosphite, diorganophosphite,triorganophosphite and organopolyphosphite compounds. Suchorganophosphite ligands employable in this invention and/or methods fortheir preparation are well known in the art.

Representative monoorganophosphites may include those having theformula: ##STR1## wherein R¹ represents a substituted or unsubstitutedtrivalent hydrocarbon radical containing from 4 to 40 carbon atoms orgreater, such as trivalent acyclic and trivalent cyclic radicals, e.g.,trivalent alkylene radicals such as those derived from1,2,2-trimethylolpropane and the like, or trivalent cycloalkyleneradicals such as those derived from 1,3,5-trihydroxycyclohexane, and thelike. Such monoorganophosphites may be found described in greaterdetail, for example, in U.S. Pat. No. 4,567,306, the disclosure of whichis incorporated herein by reference thereto.

Representative diorganophosphites may include those having the formula:##STR2## wherein R² represents a substituted or unsubstituted divalenthydrocarbon radical containing from 4 to 40 carbon atoms or greater andW represents a substituted or unsubstituted monovalent hydrocarbonradical containing from 1 to 18 carbon atoms or greater.

Representative substituted and unsubstituted monovalent hydrocarbonradicals represented by W in the above Formula (II) include alkyl andaryl radicals, while representative substituted and unsubstituteddivalent hydrocarbon radicals represented by R² include divalent acyclicradicals and divalent aromatic radicals. Illustrative divalent acyclicradicals include, for example, alkylene, alkylene-oxy-alkylene,alkylene-NR⁴ -alkylene wherein R⁴ is hydrogen or a substituted orunsubstituted monovalent hydrocarbon radical, e.g., an alkyl radicalhaving 1 to 4 carbon atoms; alkylene-S-alkylene, and cycloalkyleneradicals, and the like. The more preferred divalent acyclic radicals arethe divalent alkylene radicals such as disclosed more fully, forexample, in U.S. Pat. Nos. 3,415,906 and 4,567,302 and the like, thedisclosures of which are incorporated herein by reference. Illustrativedivalent aromatic radicals include, for example, arylene, bisarylene,arylene-alkylene, arylene-alkylene-arylene, arylene-oxy-arylene,arylene-NR⁴ -arylene wherein R⁴ is as defined above, arylene-S-arylene,and arylene-S-alkylene, and the like. More preferably R² is a divalentaromatic radical such as disclosed more fully, for example, in U.S. Pat.Nos. 4,599,206, 4,717,775, 4,835,299, and the like, the disclosures ofwhich are incorporated herein by reference.

Representative of a more preferred class of diorganophosphites are thoseof the formula: ##STR3## wherein W is as defined above, each Ar is thesame or different and represents a substituted or unsubstituted arylradical, each y is the same or different and is a value of 0 or 1, Qrepresents a divalent bridging group selected from --C(R³)₂ --, --O--,--S--, --NR⁴ --, Si(R⁵)₂ -- and --CO--, wherein each R³ is the same ordifferent and represents hydrogen, an alkyl radical having from 1 to 12carbon atoms, phenyl, tolyl, and anisyl, R⁴ is as defined above, each R⁵is the same or different and represents hydrogen or a methyl radical,and m is a value of 0 or 1. Such diorganophosphites are described ingreater detail, for example, in U.S. Pat. Nos. 4,599,206, 4,717,775, and4,835,299 the disclosures of which are incorporated herein by reference.

Representative triorganophosphites may include those having the formula:##STR4## wherein each R⁶ is the same or different and is a substitutedor unsubstituted monovalent hydrocarbon radical e.g., an alkyl,cycloalkyl, aryl, alkaryl and aralkyl radicals which may contain from 1to 24 carbon atoms. Illustrative triorganophosphites include, forexample, trialkyl phosphites, dialkylaryl phosphites, alkyldiarylphosphites, triaryl phosphites, and the like, such as, for example,trimethyl phosphite, triethyl phosphite, butyldiethyl phosphite,tri-n-propyl phosphite, tri-n-butyl phosphite, tri-2-ethylhexylphosphite, tri-n-octyl phosphite, tri-n-dodecyl phosphite,dimethylphenyl phosphite, diethylphenyl phosphite, methyldiphenylphosphite, ethyldiphenyl phosphite, triphenyl phosphite, trinaphthylphosphite, bis(3,6,8-tri-t-butyl-2-naphthyl)methylphosphite,bis(3,6,8-tri-t-butyl-2-naphthyl)cyclohexylphosphite,tris(3,6-di-t-butyl-2-naphthyl)phosphite,bis(3,6,8-tri-t-butyl-2-naphthyl)(4-biphenyl)phosphite,bis(3,6,8-tri-t-butyl-2-naphthyl)phenylphosphite,bis(3,6,8-tri-t-butyl-2-naphthyl)(4-benzoylphenyl)phosphite,bis(3,6,8-tri-t-butyl-2-naphthyl)(4-sulfonylphenyl)phosphite, and thelike. The most preferred triorganophosphite is triphenylphosphite. Suchtriorganophosphites are described in greater detail, for example, inU.S. Pat. Nos. 3,527,809 and 5,277,532, the disclosures of which areincorporated herein by reference.

Representative organopolyphosphites contain two or more tertiary(trivalent) phosphorus atoms and may include those having the formula:##STR5## wherein X represents a substituted or unsubstituted n-valentorganic bridging radical containing from 2 to 40 carbon atoms, each R⁷is the same or different and represents a divalent organic radicalcontaining from 4 to 40 carbon atoms, each R⁸ is the same or differentand represents a substituted or unsubstituted monovalent hydrocarbonradical containing from 1 to 24 carbon atoms, a and b can be the same ordifferent and each have a value of 0 to 6, with the proviso that the sumof a+b is 2 to 6 and n equals a+b. Of course it is to be understood thatwhen a has a value of 2 or more, each R⁷ radical may be the same ordifferent. Each R⁸ radical may also be the same or different any givencompound.

Representative n-valent (preferably divalent) organic bridging radicalsrepresented by X and representative divalent organic radicalsrepresented by R⁷ above, include both acyclic radicals and aromaticradicals, such as alkylene, alkylene-Q_(m) -alkylene, cycloalkylene,arylene, bisarylene, arylene-alkylene, and arylene-(CH₂)_(y) -Q_(m)-(CH₂)_(y) -arylene radicals, and the like, wherein each Q, y and m areas defined above in Formula (III). The more preferred acyclic radicalsrepresented by X and R⁷ above are divalent alkylene radicals, while themore preferred aromatic radicals represented by X and R⁷ above aredivalent arylene and bisarylene radicals, such as disclosed more fully,for example, in U.S. Pat. Nos. 4,769,498; 4,774,361: 4,885,401;5,179,055; 5,113,022; 5,202,297; 5,235,113; 5,264,616 and 5,364,950, andEuropean Patent Application Publication No. 662,468, and the like, thedisclosures of which are incorporated herein by reference.Representative preferred monovalent hydrocarbon radicals represented byeach R⁸ radical above include alkyl and aromatic radicals.

Illustrative preferred organopolyphosphites may include bisphosphitessuch as those of Formulas (VI) to (VIII) below: ##STR6## wherein eachR⁷, R⁸ and X of Formulas (VI) to (VIII) are the same as defined abovefor Formula (V). Preferably each R⁷ and X represents a divalenthydrocarbon radical selected from alkylene, arylene,arylene-alkylene-arylene, and bisarylene, while each R⁸ radicalrepresents a monovalent hydrocarbon radical selected from alkyl and arylradicals. Organophosphite ligands of such Formulas (V) to (VIII) may befound disclosed, for example, in U.S. Pat. Nos. 4,668,651; 4,748,261;4,769,498; 4,774,361; 4,885,401; 5,113,022; 5,179,055; 5,202,297;5,235,113; 5,254,741; 5,264,616; 5,312,996; 5,364,950; and 5,391,801;the disclosures of all of which are incorporated herein by reference.

Representative of more preferred classes of organobisphosphites arethose of the following Formulas (IX) to (XI) ##STR7## wherein Ar, Q, R⁷,R⁸, X, m, and y are as defined above. Most preferably X represents adivalent aryl-(CH₂)_(y) -(Q)_(m) -(CH₂)_(y) -aryl radical wherein each yindividually has a value of 0 or 1; m has a value of 0 or 1 and Q is--O--, --S-- or --C(R³)₂ where each R³ is the same or different andrepresents hydrogen or a methyl radical. More preferably each alkylradical of the above defined R⁸ groups may contain from 1 to 24 carbonatoms and each aryl radical of the above-defined Ar, X, R⁷ and R⁸ groupsof the above Formulas (IX) to (XI) may contain from 6 to 18 carbon atomsand said radicals may be the same or different, while the preferredalkylene radicals of X may contain from 2 to 18 carbon atoms and thepreferred alkylene radicals of R⁷ may contain from 5 to 18 carbon atoms.In addition, preferably the divalent Ar radicals and divalent arylradicals of X of the above formulas are phenylene radicals in which thebridging group represented by --(CH₂)_(y) --(Q)_(m) --(CH₂)_(y) -- isbonded to said phenylene radicals in positions that are ortho to theoxygen atoms of the formulas that connect the phenylene radicals totheir phosphorus atom of the formulae. It is also preferred that anysubstituent radical when present on such phenylene radicals be bonded inthe para and/or ortho position of the phenylene radicals in relation tothe oxygen atom that bonds the given substituted phenylene radical toits phosphorus atom.

Of course any of the R¹, R², R⁶, R⁷, R⁸, W, X, Q and Ar radicals of suchorganophosphites of Formulas (I) to (XI) above may be substituted ifdesired, with any suitable substituent containing from 1 to 30 carbonatoms that does not unduly adversely affect the desired result of theprocess of this invention. Substituents that may be on said radicals inaddition of course to corresponding hydrocarbon radicals such as alkyl,aryl, aralkyl, alkaryl and cyclohexyl substituents, may include forexample silyl radicals such as --Si(R¹⁰)₃ ; amino radicals such as--N(R¹⁰)₂ ; phosphine radicals such as --aryl-P(R¹⁰)₂ ; acyl radicalssuch as --C(O)R¹⁰ acyloxy radicals such as --OC(O)R¹⁰ ; amido radicalssuch as --CON(R¹⁰)₂ and --N(R¹⁰)COR¹⁰ ; sulfonyl radicals such as --SO₂R¹⁰, alkoxy radicals such as --OR¹⁰ ; sulfinyl radicals such as --SOR¹⁰,sulfenyl radicals such as --SR¹⁰, phosphonyl radicals such as--P(O)(R¹⁰)₂, as well as halogen, nitro, cyano, trifluoromethyl, hydroxyradicals, and the like, wherein each R¹⁰ radical individually representsthe same or different monovalent hydrocarbon radical having from 1 to 18carbon atoms (e.g., alkyl, aryl, aralkyl, alkaryl and cyclohexylradicals), with the proviso that in amino substituents such as --N(R¹⁰)₂each R¹⁰ taken together can also represent a divalent bridging groupthat forms a heterocyclic radical with the nitrogen atom, and in amidosubstituents such as --C(O)N(R¹⁰)₂ and --N(R¹⁰)COR¹⁰ each R¹⁰ bonded toN can also be hydrogen. Of course it is to be understood that any of thesubstituted or unsubstituted hydrocarbon radicals groups that make up aparticular given organophosphite may be the same or different.

More specifically illustrative substituents include primary, secondaryand tertiary alkyl radicals such as methyl, ethyl, n-propyl, isopropyl,butyl, sec-butyl, t-butyl, neo-pentyl, n-hexyl, amyl, sec-amyl, t-amyl,iso-octyl, decyl, octadecyl, and the like; aryl radicals such as phenyl,naphthyl and the like; aralkyl radicals such as benzyl, phenylethyl,triphenylmethyl, and the like; alkaryl radicals such as tolyl, xylyl,and the like; alicyclic radicals such as cyclopentyl, cyclohexyl,1-methylcyclohexyl, cyclooctyl, cyclohexylethyl, and the like; alkoxyradicals such as methoxy, ethoxy, propoxy, t-butoxy, --OCH₂ CH₂ OCH₃,--O(CH₂ CH₂)₂ OCH₃, --O(CH₂ CH₂)₃ OCH₃, and the like; aryloxy radicalssuch as phenoxy and the like; as well as silyl radicals such as--Si(CH₃)₃, --Si(OCH₃)₃, --Si(C₃ H₇)₃, and the like; amino radicals suchas --NH₂, --N(CH₃)₂, --NHCH₃, --NH(C₂ H₅), and the like; arylphosphineradicals such as --P(C₆ H₅)₂, and the like; acyl radicals such as--C(O)CH₃, --C(O)C₂ H₅, --C(O)C₆ H₅, and the like; carbonyloxy radicalssuch as --C(O)OCH₃ and the like; oxycarbonyl radicals such as --O(CO)C₆H₅, and the like; amido radicals such as --CONH₂, --CON(CH₃)₂,--NHC(O)CH₃, and the like; sulfonyl radicals such as --S(O)₂ C₂ H₅ andthe like; sulfinyl radicals such as --S(O)CH₃ and the like; sulfenylradicals such as --SCH₃, --SC₂ H₅, --SC₆ H₅, and the like; phosphonylradicals such as --P(O)(C₆ H₅)₂, --P(O)(CH₃)₂, --P(O)(C₂ H₅)₂, --P(O)(C₃H₇)₂, --P(O)(C₄ H₉)₂, --P(O)(C₆ H₁₃)₂, --P(O)CH₃ (C₆ H₅), --P(O)(H)(C₆H₅), and the like.

Specific illustrative examples of such organophosphite ligands includethe following: ##STR8##

As noted above, the metal-organophosphite ligand complex catalystsemployable in this invention may be formed by methods known in the art.The metal-organophosphite ligand complex catalysts may be in homogeneousor heterogeneous form. For instance, preformed rhodiumhydrido-carbonyl-organophosphite ligand catalysts may be prepared andintroduced into the reaction mixture of a hydroformylation process. Morepreferably, the rhodium-organophosphite ligand complex catalysts can bederived from a rhodium catalyst precursor which may be introduced intothe reaction medium for in situ formation of the active catalyst. Forexample, rhodium catalyst precursors such as rhodium dicarbonylacetylacetonate, Rh₂ O₃, Rh₄ (CO)₁₂, Rh₆ (CO)₁₆, Rh(NO₃)₃ and the likemay be introduced into the reaction mixture along with theorganophosphite ligand for the in situ formation of the active catalyst.In a preferred embodiment of this invention, rhodium dicarbonylacetylacetonate is employed as a rhodium precursor and reacted in thepresence of a solvent with the organophosphite ligand to form acatalytic rhodium-organophosphite ligand complex precursor which isintroduced into the reactor along with excess (free) organophosphiteligand for the in situ formation of the active catalyst. In any event,it is sufficient for the purpose of this invention that carbon monoxide,hydrogen and organophosphite compound are all ligands that are capableof being complexed with the metal and that an activemetal-organophosphite ligand catalyst is present in the reaction mixtureunder the conditions used in the hydroformylation reaction.

More particularly, a catalyst precursor composition can be formedconsisting essentially of a solubilized metal-organophosphite ligandcomplex precursor catalyst, an organic solvent and free organophosphiteligand. Such precursor compositions may be prepared by forming asolution of a rhodium starting material, such as a rhodium oxide,hydride, carbonyl or salt, e.g. a nitrate, which may or may not be incomplex combination with a organophosphite ligand as defined herein. Anysuitable rhodium starting material may be employed, e.g. rhodiumdicarbonyl acetylacetonate, Rh₂ O₃, Rh₄ (CO)₁₂, Rh₆ (CO)₁₆, Rh(NO₃)₃,and organophosphite ligand rhodium carbonyl hydrides. Carbonyl andorganophosphite ligands, if not already complexed with the initialrhodium, may be complexed to the rhodium either prior to or in situduring the hydroformylation process.

By way of illustration, the preferred catalyst precursor composition ofthis invention consists essentially of a solubilized rhodium carbonylorganophosphite ligand complex precursor catalyst, a solvent andoptionally free organophosphite ligand prepared by forming a solution ofrhodium dicarbonyl acetylacetonate, an organic solvent and aorganophosphite ligand as defined herein. The organophosphite ligandreadily replaces one of the carbonyl ligands of the rhodiumacetylacetonate complex precursor at room temperature as witnessed bythe evolution of carbon monoxide gas. This substitution reaction may befacilitated by heating the solution if desired. Any suitable organicsolvent in which both the rhodium dicarbonyl acetylacetonate complexprecursor and rhodium organophosphite ligand complex precursor aresoluble can be employed. The amounts of rhodium complex catalystprecursor, organic solvent and organophosphite ligand, as well as theirpreferred embodiments present in such catalyst precursor compositionsmay obviously correspond to those amounts employable in thehydroformylation process of this invention. Experience has shown thatthe acetylacetonate ligand of the precursor catalyst is replaced afterthe hydroformylation process has begun with a different ligand, e.g.,hydrogen, carbon monoxide or organophosphite ligand, to form the activecomplex catalyst as explained above. The acetylacetone which is freedfrom the precursor catalyst under hydroformylation conditions is removedfrom the reaction medium with the product aldehyde and thus is in no waydetrimental to the hydroformylation process. The use of such preferredrhodium complex catalytic precursor compositions provides a simpleeconomical and efficient method for handling the rhodium precursor andhydroformylation start-up.

Accordingly, the metal-organophosphite ligand complex catalysts used inthe process of this invention consists essentially of the metalcomplexed with carbon monoxide and a organophosphite ligand, said ligandbeing bonded (complexed) to the metal in a chelated and/or non-chelatedfashion. Moreover, the terminology "consists essentially of", as usedherein, does not exclude, but rather includes, hydrogen complexed withthe metal, in addition to carbon monoxide and the organophosphiteligand. Further, such terminology does not exclude the possibility ofother organic ligands and/or anions that might also be complexed withthe metal. Materials in amounts which unduly adversely poison or undulydeactivate the catalyst are not desirable and so the catalyst mostdesirably is free of contaminants such as metal-bound halogen (e.g.,chlorine, and the like) although such may not be absolutely necessary.The hydrogen and/or carbonyl ligands of an active metal-organophosphiteligand complex catalyst may be present as a result of being ligandsbound to a precursor catalyst and/or as a result of in situ formation,e.g., due to the hydrogen and carbon monoxide gases employed inhydroformylation process of this invention.

As noted the hydroformylation processes of this invention involve theuse of a metal-organophosphite ligand complex catalyst as describedherein. Of course mixtures of such catalysts can also be employed ifdesired. The amount of metal-organophosphite ligand complex catalystpresent in the reaction medium of a given hydroformylation processencompassed by this invention need only be that minimum amount necessaryto provide the given metal concentration desired to be employed andwhich will furnish the basis for at least the catalytic amount of metalnecessary to catalyze the particular hydroformylation process involvedsuch as disclosed, for example, in the above-mentioned patents. Ingeneral, metal, e.g., rhodium, concentrations in the range of from about10 parts per million to about 1000 parts per million, calculated as freerhodium, in the hydroformylation reaction medium should be sufficientfor most processes, while it is generally preferred to employ from about10 to 500 parts per million of metal, e.g., rhodium, and more preferablyfrom 25 to 350 parts per million of metal, e.g., rhodium.

In addition to the metal-organophosphite ligand complex catalyst, freeorganophosphite ligand (i.e., ligand that is not complexed with themetal) may also be present in the hydroformylation reaction medium. Thefree organophosphite ligand may correspond to any of the above-definedorganophosphite ligands discussed above as employable herein. It ispreferred that the free organophosphite ligand be the same as theorganophosphite ligand of the metal-organophosphite ligand complexcatalyst employed. However, such ligands need not be the same in anygiven process. The hydroformylation process of this invention mayinvolve from about 0.1 moles or less to about 100 moles or higher, offree organophosphite ligand per mole of metal in the hydroformylationreaction medium. Preferably the hydroformylation process of thisinvention is carried out in the presence of from about 1 to about 50moles of organophosphite ligand, and more preferably fororganopolyphosphites from about 1.1 to about 4 moles oforganopolyphosphite ligand, per mole of metal present in the reactionmedium; said amounts of organophosphite ligand being the sum of both theamount of organophosphite ligand that is bound (complexed) to the metalpresent and the amount of free (non-complexed) organophosphite ligandpresent. Since it is more preferred to produce non-optically activealdehydes by hydroformylating achiral olefins, the more preferredorganophosphite ligands are achiral type organophosphite ligands,especially those encompassed by Formula (V) above, and more preferablythose of Formulas (VI) and (IX) above. Of course, if desired, make-up oradditional organophosphite ligand can be supplied to the reaction mediumof the hydroformylation process at any time and in any suitable manner,e.g. to maintain a predetermined level of free ligand in the reactionmedium.

As indicated above, the hydroformylation catalyst may be inheterogeneous form during the reaction and/or during the productseparation. Such catalysts are particularly advantageous in thehydroformylation of olefins to produce high boiling or thermallysensitive aldehydes, so that the catalyst may be separated from theproducts by filtration or decantation at low temperatures. For example,the rhodium catalyst may be attached to a support so that the catalystretains its solid form during both the hydroformylation and separationstages, or is soluble in a liquid reaction medium at high temperaturesand then is precipitated on cooling.

As an illustration, the rhodium catalyst may be impregnated onto anysolid support, such as inorganic oxides, (i.e. alumina, silica, titania,or zirconia) carbon, or ion exchange resins. The catalyst may besupported on, or intercalated inside the pores of, a zeolite, glass orclay; the catalyst may also be dissolved in a liquid film coating thepores of said zeolite or glass. Such zeolite-supported catalysts areparticularly advantageous for producing one or more regioisomericaldehydes in high selectivity, as determined by the pore size of thezeolite. The techniques for supporting catalysts on solids, such asincipient wetness, which will be known to those skilled in the art. Thesolid catalyst thus formed may still be complexed with one or more ofthe ligands defined above. Descriptions of such solid catalysts may befound in for example: J. Mol. Cat. 1991, 70, 363-368; Catal. Lett. 1991,8, 209-214; J. Organomet. Chem, 1991, 403, 221-227; Nature, 1989, 339,454-455; J. Catal. 1985, 96, 563-573; J. Mol. Cat. 1987, 39, 243-259.

The metal, e.g., rhodium, catalyst may be attached to a thin film ormembrane support, such as cellulose acetate or polyphenylenesulfone, asdescribed in for example J. Mol. Cat. 1990, 63, 213-221.

The metal, e.g., rhodium, catalyst may be attached to an insolublepolymeric support through an organophosphorus-containing ligand, such asa phosphite, incorporated into the polymer. The supported catalyst isnot limited by the choice of polymer or phosphorus-containing speciesincorporated into it. Descriptions of polymer-supported catalysts may befound in for example: J. Mol. Cat. 1993, 83, 17-35; Chemtech 1983, 46;J. Am. Chem. Soc. 1987, 109, 7122-7127.

In the heterogeneous catalysts described above, the catalyst may remainin its heterogeneous form during the entire hydroformylation andcatalyst separation process. In another embodiment of the invention, thecatalyst may be supported on a polymer which, by the nature of itsmolecular weight, is soluble in the reaction medium at elevatedtemperatures, but precipitates upon cooling, thus facilitating catalystseparation from the reaction mixture. Such "soluble" polymer-supportedcatalysts are described in for example: Polymer, 1992, 33, 161; J. Org.Chem. 1989, 54, 2726-2730.

More preferably, the reaction is carried out in the slurry phase due tothe high boiling points of the products, and to avoid decomposition ofthe product aldehydes. The catalyst may then be separated from theproduct mixture, for example, by filtration or decantation. The reactionproduct fluid may contain a heterogeneous metal-organophosphite ligandcomplex catalyst, e.g., slurry, or at least a portion of the reactionproduct fluid may contact a fixed heterogeneous metal-organophosphiteligand complex catalyst during the hydroformylation process. In anembodiment of this invention, the metal-organophosphite ligand complexcatalyst may be slurried in the reaction product fluid.

The substituted or unsubstituted olefinic unsaturated starting materialreactants that may be employed in the hydroformylation processes of thisinvention include both optically active (prochiral and chiral) andnon-optically active (achiral) olefinic unsaturated compounds containingfrom 2 to 40, preferably 4 to 20, carbon atoms. Such olefinicunsaturated compounds can be terminally or internally unsaturated and beof straight-chain, branched chain or cyclic structures, as well asolefin mixtures, such as obtained from the oligomerization of propene,butene, isobutene, etc. (such as so called dimeric, trimeric ortetrameric propylene and the like, as disclosed, for example, in U.S.Pat. Nos. 4,518,809 and 4,528,403). Moreover, such olefin compounds mayfurther contain one or more ethylenic unsaturated groups, and of course,mixtures of two or more different olefinic unsaturated compounds may beemployed as the starting hydroformylation material if desired. Forexample, commercial alpha olefins containing four or more carbon atomsmay contain minor amounts of corresponding internal olefins and/or theircorresponding saturated hydrocarbon and that such commercial olefinsneed not necessarily be purified from same prior to beinghydroformylated. Illustrative mixtures of olefinic starting materialsthat can be employed in the hydroformylation reactions include, forexample, mixed butenes, e.g., Raffinate I and II. Further such olefinicunsaturated compounds and the corresponding aldehyde products derivedtherefrom may also contain one or more groups or substituents which donot unduly adversely affect the hydroformylation process or the processof this invention such as described, for example, in U.S. Pat. Nos.3,527,809, 4,769,498 and the like.

Most preferably the subject invention is especially useful for theproduction of non-optically active aldehydes, by hydroformylatingachiral alpha-olefins containing from 2 to 30, preferably 4 to 20,carbon atoms, and achiral internal olefins containing from 4 to 20carbon atoms as well as starting material mixtures of such alpha olefinsand internal olefins.

Illustrative alpha and internal olefins include, for example, ethylene,propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene,1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene,2-butene, 2-methyl propene (isobutylene), 2-methylbutene, 2-pentene,2-hexene, 3-hexane, 2-heptene, 2-octene, cyclohexene, propylene dimers,propylene trimers, propylene tetramers, butadiene, piperylene, isoprene,2-ethyl-1-hexene, styrene, 4-methyl styrene, 4-isopropyl styrene,4-tert-butyl styrene, alpha-methyl styrene, 4-tert-butyl-alpha-methylstyrene, 1,3-diisopropenylbenzene, 3-phenyl-1-propene, 1,4-hexadiene,1,7-octadiene, 3-cyclohexyl-1-butene, and the like, as well as,1,3-dienes, butadiene, alkyl alkenoates, e.g., methyl pentenoate,alkenyl alkanoates, alkenyl alkyl ethers, alkenols, e.g., pentenols,alkenals, e.g., pentenals, and the like, such as allyl alcohol, allylbutyrate, hex-1-en-4-ol, oct-1-en-4-ol, vinyl acetate, allyl acetate,3-butenyl acetate, vinyl propionate, allyl propionate, methylmethacrylate, vinyl ethyl ether, vinyl methyl ether, allyl ethyl ether,n-propyl-7-octenoate, 3-butenenitrile, 5-hexenamide, eugenol,iso-eugenol, safrole, iso-safrole, anethol, 4-allylanisole, indene,limonene, beta-pinene, dicyclopentadiene, cyclooctadiene, camphene,linalool, and the like.

Prochiral and chiral olefins useful in the asymmetric hydroformylationthat can be employed to produce enantiomeric aldehyde mixtures that maybe encompassed by in this invention include those represented by theformula: ##STR9## wherein R₁, R₂, R₃ and R₄ are the same or different(provided R₁ is different from R₂ or R₃ is different from R₄) and areselected from hydrogen; alkyl; substituted alkyl, said substitutionbeing selected from dialkylamino such as benzylamino and dibenzylamino,alkoxy such as methoxy and ethoxy, acyloxy such as acetoxy, halo, nitro,nitrile, thio, carbonyl, carboxamide, carboxaldehyde, carboxyl,carboxylic ester; aryl including phenyl; substituted aryl includingphenyl, said substitution being selected from alkyl, amino includingalkylamino and dialkylamino such as benzylamino and dibenzylamino,hydroxy, alkoxy such as methoxy and ethoxy, acyloxy such as acetoxy,halo, nitrile, nitro, carboxyl, carboxaldehyde, carboxylic ester,carbonyl, and thio; acyloxy such as acetoxy; alkoxy such as methoxy andethoxy; amino including alkylamino and dialkylamino such as benzylaminoand dibenzylamino; acylamino and diacylamino such as acetylbenzylaminoand diacetylamino; nitro; carbonyl; nitrile; carboxyl; carboxamide;carboxaldehyde; carboxylic ester; and alkylmercapto such asmethylmercapto. It is understood that the prochiral and chiral olefinsof this definition also include molecules of the above general formulawhere the R groups are connected to form ring compounds, e.g.,3-methyl-1-cyclohexene, and the like.

Illustrative optically active or prochiral olefinic compounds useful inasymmetric hydroformylation include, for example, p-isobutylstyrene,2-vinyl-6-methoxy-2-naphthylene, 3-ethenylphenyl phenyl ketone,4-ethenylphenyl-2-thienylketone, 4-ethenyl-2-fluorobiphenyl,4-(1,3-dihydro-1-oxo-2H-isoindol-2-yl)styrene,2-ethenyl-5-benzoylthiophene, 3-ethenylphenyl phenyl ether,propenylbenzene, isobutyl-4-propenylbenzene, phenyl vinyl ether and thelike. Other olefinic compounds include substituted aryl ethylenes asdescribed, for example, in U.S. Pat. Nos. 4,329,507, 5,360,938 and5,491,266, the disclosures of which are incorporated herein byreference.

Illustrative of suitable substituted and unsubstituted olefinic startingmaterials include those permissible substituted and unsubstitutedolefinic compounds described in Kirk-Othmer, Encyclopedia of ChemicalTechnology, Fourth Edition, 1996, the pertinent portions of which areincorporated herein by reference.

The reaction conditions of the hydroformylation processes encompassed bythis invention may include any suitable type hydroformylation conditionsheretofore employed for producing optically active and/or non-opticallyactive aldehydes. For instance, the total gas pressure of hydrogen,carbon monoxide and olefin starting compound of the hydroformylationprocess may range from about 1 to about 10,000 psia. In general,however, it is preferred that the process be operated at a total gaspressure of hydrogen, carbon monoxide and olefin starting compound ofless than about 2000 psia and more preferably less than about 500 psia.The minimum total pressure is limited predominately by the amount ofreactants necessary to obtain a desired rate of reaction. Morespecifically the carbon monoxide partial pressure of thehydroformylation process of this invention is preferable from about 1 toabout 1000 psia, and more preferably from about 3 to about 800 psia,while the hydrogen partial pressure is preferably about 5 to about 500psia and more preferably from about 10 to about 300 psia. In general H₂:CO molar ratio of gaseous hydrogen to carbon monoxide may range fromabout 1:10 to 100:1 or higher, the more preferred hydrogen to carbonmonoxide molar ratio being from about 1:10 to about 10:1. Further, thehydroformylation process may be conducted at a reaction temperature fromabout -25° C. to about 200° C. In general hydroformylation reactiontemperatures of about 50° C. to about 120° C. are preferred for alltypes of olefinic starting materials. Of course it is to be understoodthat when non-optically active aldehyde products are desired, achiraltype olefin starting materials and organophosphite ligands are employedand when optically active aldehyde products are desired prochiral orchiral type olefin starting materials and organophosphite ligands areemployed. Of course, it is to be also understood that thehydroformylation reaction conditions employed will be governed by thetype of aldehyde product desired.

The hydroformylation processes encompassed by this invention are alsoconducted in the presence of an organic solvent for themetal-organophosphite ligand complex catalyst and free organophosphiteligand. The solvent may also contain dissolved water up to thesaturation limit. Depending on the particular catalyst and reactantsemployed, suitable organic solvents include, for example, alcohols,alkanes, alkenes, alkynes, ethers, aldehydes, higher boiling aldehydecondensation byproducts, ketones, esters, amides, tertiary amines,aromatics and the like. Any suitable solvent which does not undulyadversely interfere with the intended hydroformylation reaction can beemployed and such solvents may include those disclosed heretoforecommonly employed in known metal catalyzed hydroformylation reactions.Mixtures of one or more different solvents may be employed if desired.In general, with regard to the production of achiral (non-opticallyactive) aldehydes, it is preferred to employ aldehyde compoundscorresponding to the aldehyde products desired to be produced and/orhigher boiling aldehyde liquid condensation byproducts as the mainorganic solvents as is common in the art. Such aldehyde condensationbyproducts can also be preformed if desired and used accordingly.Illustrative preferred solvents employable in the production ofaldehydes include ketones (e.g. acetone and methylethyl ketone), esters(e.g. ethyl acetate), hydrocarbons (e.g. toluene), nitrohydrocarbons(e.g. nitrobenzene), ethers (e.g. tetrahydrofuran (THF) and sulfolane.Suitable solvents are disclosed in U.S. Pat. No. 5,312,996. The amountof solvent employed is not critical to the subject invention and needonly be that amount sufficient to solubilize the catalyst and freeligand of the hydroformylation reaction mixture to be treated. Ingeneral, the amount of solvent may range from about 5 percent by weightup to about 99 percent by weight or more based on the total weight ofthe hydroformylation reaction mixture starting material.

Accordingly illustrative non-optically active aldehyde products includee.g., propionaldehyde, n-butyraldehyde, isobutyraldehyde,n-valeraldehyde, 2-methyl 1-butyraldehyde, hexanal, hydroxyhexanal,2-methyl valeraldehyde, heptanal, 2-methyl 1-hexanal, octanal, 2-methyl1-heptanal, nonanal, 2-methyl-1-octanal, 2-ethyl 1-heptanal, 3-propyl1-hexanal, decanal, adipaldehyde, 2-methylglutaraldehyde,2-methyladipaldehyde, 3-methyladipaldehyde, 3-hydroxypropionaldehyde,6-hydroxyhexanal, alkenals, e.g., 2-, 3- and 4-pentenal, alkyl5-formylvalerate, 2-methyl-1-nonanal, undecanal, 2-methyl 1-decanal,dodecanal, 2-methyl 1-undecanal, tridecanal, 2-methyl 1-tridecanal,2-ethyl, 1-dodecanal, 3-propyl-1-undecanal, pentadecanal,2-methyl-1-tetradecanal, hexadecanal, 2-methyl-1-pentadecanal,heptadecanal, 2-methyl-1-hexadecanal, octadecanal,2-methyl-1-heptadecanal, nonodecanal, 2-methyl-1-octadecanal, 2-ethyl1-heptadecanal, 3-propyl-1-hexadecanal, eicosanal,2-methyl-1-nonadecanal, heneicosanal, 2-methyl-1-eicosanal, tricosanal,2-methyl-1-docosanal, tetracosanal, 2-methyl-1-tricosanal, pentacosanal,2-methyl-1-tetracosanal, 2-ethyl 1-tricosanal, 3-propyl-1-docosanal,heptacosanal, 2-methyl-1-octacosanal, nonacosanal,2-methyl-1-octacosanal, hentriacontanal, 2-methyl-1-triacontanal, andthe like.

Illustrative optically active aldehyde products include (enantiomeric)aldehyde compounds prepared by the asymmetric hydroformylation processof this invention such as, e.g. S-2-(p-isobutylphenyl)-propionaldehyde,S-2-(6-methoxy-2-naphthyl)propionaldehyde,S-2-(3-benzoylphenyl)-propionaldehyde,S-2-(p-thienoylphenyl)propionaldehyde,S-2-(3-fluoro-4-phenyl)phenylpropionaldehyde, S-2-4-(1,3-dihydro-1-oxo-2H-isoindol-2-yl)phenyl!propionaldehyde,S-2-(2-methylacetaldehyde)-5-benzoylthiophene and the like.

Illustrative of suitable substituted and unsubstituted aldehyde productsinclude those permissible substituted and unsubstituted aldehydecompounds described in Kirk-Othmer, Encyclopedia of Chemical Technology,Fourth Edition, 1996, the pertinent portions of which are incorporatedherein by reference.

As indicated above, it is generally preferred to carry out thehydroformylation processes of this invention in a continuous manner. Ingeneral, continuous hydroformylation processes are well known in the artand may involve: (a) hydroformylating the olefinic starting material(s)with carbon monoxide and hydrogen in a liquid homogeneous reactionmixture comprising a solvent, the metal-organophosphite ligand complexcatalyst, and free organophosphite ligand; (b) maintaining reactiontemperature and pressure conditions favorable to the hydroformylation ofthe olefinic starting material(s); (c) supplying make-up quantities ofthe olefinic starting material(s), carbon monoxide and hydrogen to thereaction medium as those reactants are used up; and (d) recovering thedesired aldehyde hydroformylation product(s) in any manner desired. Thecontinuous process can be carried out in a single pass mode, i.e.,wherein a vaporous mixture comprising unreacted olefinic startingmaterial(s) and vaporized aldehyde product is removed from the liquidreaction mixture from whence the aldehyde product is recovered andmake-up olefinic starting material(s), carbon monoxide and hydrogen aresupplied to the liquid reaction medium for the next single pass throughwithout recycling the unreacted olefinic starting material(s). Suchtypes of recycle procedure are well known in the art and may involve theliquid recycling of the metal-organophosphite complex catalyst fluidseparated from the desired aldehyde reaction product(s), such asdisclosed, for example, in U.S. Pat. No. 4,148,830 or a gas recycleprocedure such as disclosed, for example, in U.S. Pat. No. 4,247,486, aswell as a combination of both a liquid and gas recycle procedure ifdesired. The disclosures of said U.S. Pat. Nos. 4,148,830 and 4,247,486are incorporated herein by reference thereto. The most preferredhydroformylation process of this invention comprises a continuous liquidcatalyst recycle process. Suitable liquid catalyst recycle proceduresare disclosed, for example, in U.S. Pat. Nos. 4,668,651; 4,774,361;5,102,505 and 5,110,990.

In an embodiment of this invention, the aldehyde product mixtures may beseparated from the other components of the crude reaction mixtures inwhich the aldehyde mixtures are produced by any suitable method.Suitable separation methods include, for example, solvent extraction,crystallization, distillation, vaporization, wiped film evaporation,falling film evaporation, phase separation, filtration and the like. Itmay be desired to remove the aldehyde products from the crude reactionmixture as they are formed through the use of trapping agents asdescribed in published Patent Cooperation Treaty Patent Application WO88/08835. A preferred method for separating the aldehyde mixtures fromthe other components of the crude reaction mixtures is by membraneseparation. Such membrane separation can be achieved as set out in U.S.Pat. No. 5,430,194 and copending U.S. patent application Ser. No.08/430,790, filed May 5, 1995, referred to above.

As indicated above, at the conclusion of (or during) the process of thisinvention, the desired aldehydes may be recovered from the reactionmixtures used in the process of this invention. For example, therecovery techniques disclosed in U.S. Pat. Nos. 4,148,830 and 4,247,486can be used. For instance, in a continuous liquid catalyst recycleprocess the portion of the liquid reaction mixture (containing aldehydeproduct, catalyst, etc.), i.e., reaction product fluid, removed from thereaction zone can be passed to a separation zone, e.g.,vaporizer/separator, wherein the desired aldehyde product can beseparated via distillation, in one or more stages, under normal, reducedor elevated pressure, from the liquid reaction fluid, condensed andcollected in a product receiver, and further purified if desired. Theremaining non-volatilized catalyst containing liquid reaction mixturemay then be recycled back to the reactor as may if desired any othervolatile materials, e.g., unreacted olefin, together with any hydrogenand carbon monoxide dissolved in the liquid reaction after separationthereof from the condensed aldehyde product, e.g., by distillation inany conventional manner. In general, it is preferred to separate thedesired aldehydes from the catalyst-containing reaction mixture underreduced pressure and at low temperatures so as to avoid possibledegradation of the organophosphite ligand and reaction products. When analpha-mono-olefin reactant is also employed, the aldehyde derivativethereof can also be separated by the above methods.

More particularly, distillation and separation of the desired aldehydeproduct from the metal-organophosphite complex catalyst containingreaction product fluid may take place at any suitable temperaturedesired. In general, it is recommended that such distillation take placeat relatively low temperatures, such as below 150° C., and morepreferably at a temperature in the range of from about 50° C. to about140° C. It is also generally recommended that such aldehyde distillationtake place under reduced pressure, e.g., a total gas pressure that issubstantially lower than the total gas pressure employed duringhydroformylation when low boiling aldehydes (e.g., C₄ to C₆) areinvolved or under vacuum when high boiling aldehydes (e.g. C₇ orgreater) are involved. For instance, a common practice is to subject theliquid reaction product medium removed from the hydroformylation reactorto a pressure reduction so as to volatilize a substantial portion of theunreacted gases dissolved in the liquid medium which now contains a muchlower synthesis gas concentration than was present in thehydroformylation reaction medium to the distillation zone, e.g.vaporizer/separator, wherein the desired aldehyde product is distilled.In general, distillation pressures ranging from vacuum pressures on upto total gas pressure of about 50 psig should be sufficient for mostpurposes.

As stated above, the subject invention resides in the discovery thathydrolytic decomposition and rhodium catalyst deactivation as discussedherein can be prevented or lessened by (a) treating in at least onescrubber zone at least a portion of said reaction product fluid derivedfrom said hydroformylation process and which also contains phosphorusacidic compounds formed during said hydroformylation process with watersufficient to remove at least some amount of the phosphorus acidiccompounds from said reaction product fluid and (b) treating in at leastone ion exchange zone at least a portion of the water which containsphosphorus acidic compounds removed from said reaction product fluidwith one or more ion exchange resins sufficient to remove at least someamount of the phosphorus acidic compounds from said water. Becausepassing a hydroformylation reaction product fluid directly through anion exchange resin can cause rhodium precipitation on the ion exchangeresin surface and pores, thereby causing process complications, anadvantage of this invention is that one can use the acidity removingcapability of ion exchange resins with essentially no loss of rhodium.The use of one or more water scrubbers in conjunction with one or moreion exchange resins in metal-organophosphite ligand complex catalyzedprocesses to prevent and/or lessen hydrolytic degradation of theorganophosphite ligand and deactivation of the metal-organophosphiteligand complex catalyst of such processes is disclosed in copending U.S.patent application Ser. No. 08/756,788, filed on an even date herewith,the disclosure of which is incorporated herein by reference.

The removal of at least some amount of the phosphorus acid compounds,for example, H₃ PO₃, aldehyde acids such as hydroxy alkyl phosphonicacids, H₃ PO₄ and the like, from the hydroformylation system allows oneto control the acidity of the hydroformylation reaction medium, therebystabilizing the useful organophosphite ligand by preventing or lesseningits hydrolytic decomposition. The need to control the acidity inorganophosphite promoted metal catalyzed hydroformylation was explainedabove. Thus the purpose of the subject invention is to remove or reduceexcessive acidity from the catalyst system in order to maintain a properacidity level in the reaction product fluid so that the consumption ofthe useful organophosphite ligands do not hydrolytically degrade at anunacceptable rate while keeping catalyst activity at a productive level.The subject invention submits that the best means for regulating suchacidity is to remove such phosphorus acidic materials from the reactionproduct fluid in one or more ion exchange zones containing one or moreion exchange resins. In this way the acidic materials are removed asdisclosed herein as opposed to merely being scavenged and/or neutralizedand allowed to remain in the reaction medium, thereby avoidingaccumulation of such scavenged and/or neutralized byproducts, andpreventing further possible necessary secondary chemistry or thebuilding of salt deposits in the reactor zone, separator zone and/orscrubber zone.

Said treatment of the metal-organophosphite ligand complex catalystcontaining reaction product fluid with the water may be conducted in anysuitable manner or fashion desired that does not unduly adversely affectthe basic hydroformylation process from which said reaction productfluid was derived. For instance, the water treatment may be conducted onall or any portion of the desired reaction product fluid that is to betreated and which has been removed from the at least one reaction zoneor the at least one separation zone. The treated contacted water maythen be sent to the one or more ion exchange zones or returned to the atleast one reaction zone or the at least one separation zone.Alternately, water may be sprayed into or otherwise added to the atleast one reaction zone or the at least one separation zone to achieveacidity control. The water layer formed may then be decanted from thereaction product fluid.

This invention involving the use of water is especially adaptable foruse in continuous liquid catalyst recycle hydroformylation processesthat employ the invention of U.S. Pat. No. 5,288,918, which comprisescarrying out the process in the presence of a catalytically activeenhancing additive, said additive being selected from the classconsisting of added water, a weakly acidic compound (e.g., biphenol), orboth added water and a weakly acidic compound. The enhancing additive isemployed to help selectively hydrolyze and prevent the build-up of anundesirable monophosphite byproduct that can be formed during certainprocesses and which poisons the metal catalyst as explained therein.Nonetheless, it is to be understood that a preferred hydroformylationprocess of this invention, i.e., the embodiment comprising preventingand/or lessening hydrolytic degradation of the organophosphite ligandand deactivation of the metal-organophosphite ligand complex catalyst by(a) treating in at least one scrubber zone at least a portion of thehydroformylation reaction product fluid derived from saidhydroformylation process and which also contains phosphorus acidiccompounds formed during said hydroformylation process with watersufficient to remove at least some amount of the phosphorus acidiccompounds from said reaction product fluid and (b) treating in at leastone ion exchange zone at least a portion of the water which containsphosphorus acidic compounds removed from said reaction product fluidwith one or more ion exchange resins sufficient to remove at least someamount of the phosphorus acidic compounds from said water, is stillconsidered to be essentially a "non-aqueous" process, which is to say,any water present in the hydroformylation reaction medium is not presentin an amount sufficient to cause either the hydroformylation reaction orsaid medium to be considered as encompassing a separate aqueous or waterphase or layer in addition to an organic phase.

Also, it is to be understood that another preferred hydroformylationprocess of this invention, i.e., the embodiment comprising preventingand/or lessening hydrolytic degradation of the organophosphite ligandand deactivation of the metal-organophosphite ligand complex catalyst bytreating at least a portion of the hydroformylation reaction productfluid derived from the hydroformylation process and which also containsphosphorus acidic compounds formed during said hydroformylation processby introducing one or more amines or phosphines into said at least onereaction zone and/or said at least one separation zone sufficient toremove at least some amount of the phosphorus acidic compounds from saidreaction product fluid, is also considered to be essentially a"non-aqueous" process.

Thus, for example, water may be used to treat all or part of a reactionproduct fluid of a continuous liquid catalyst recycle hydroformylationprocess that has been removed from the reaction zone at any time priorto or after separation of the aldehyde product therefrom. Morepreferably said water treatment involves treating all or part of thereaction product fluid obtained after distillation of as much of thealdehyde product desired, for example, prior to or during the recyclingof said reaction product fluid to the reaction zone. For instance, apreferred mode would be to continuously pass all or part (e.g. a slipstream) of the recycled reaction product fluid that is being recycled tothe reaction zone through a liquid extractor containing the water justbefore said catalyst containing residue is to re-enter the reactionzone.

Thus it is to be understood that the metal-organophosphite ligandcomplex catalyst containing reaction product fluid to be treated withwater may contain in addition to the catalyst complex and its organicsolvent, aldehyde product, free organophosphite ligand, unreactedolefin, and any other ingredient or additive consistent with thereaction medium of the hydroformylation process from which said reactionproduct fluids are derived.

Moreover, removal of the desired aldehyde product can causeconcentrations of the other ingredients of the reaction product fluidsto be increased proportionately. Thus for example, the organophosphiteligand concentration in the metal-organophosphite ligand complexcatalyst containing reaction product fluid to be treated by water inaccordance with the process of this invention may range from betweenabout 0.005 and 15 weight percent based on the total weight of thereaction product fluid. Preferably the ligand concentration is between0.01 and 10 weight percent, and more preferably is between about 0.05and 5 weight percent on that basis. Similarly, the concentration of themetal in the metal-organophosphite ligand complex catalyst containingreaction product fluid to be treated by the water in accordance with theprocess of this invention may be as high as about 5000 parts per millionby weight based on the weight of the reaction product fluid. Preferablythe metal concentration is between about 50 and 2500 parts per millionby weight based on the weight of the reaction product fluid, and morepreferably is between about 70 and 2000 parts per million by weightbased on the weight of the reaction product fluid.

The manner in which the metal-organophosphite ligand complex catalystcontaining reaction product fluid and water are contacted, as well assuch treatment conditions, as the amount of water, temperature, pressureand contact time are not narrowly critical and obviously need only besufficient to obtain the results desired. For instance, said treatmentmay be carried out in any suitable vessel or container, e.g. anyconventional liquid extractor, which provides a suitable means forthorough contact between the organic reaction product fluid and water,may be employed herein. In general it is preferred to pass the organicreaction product fluid through the water in a sieve tray extractorcolumn in a counter-current fashion. The amount of water employed by thesubject invention and time of contact with the reaction product fluidneed only be that which is sufficient to remove at least some amount ofthe phosphorus acidic compounds which cause hydrolytic degradation ofthe desirable organophosphite ligands. Preferably the amount of water issufficient to at least maintain the concentration of such acidiccompounds below the threshold level that causes rapid degradation of theorganophosphite ligand.

For instance, a preferred quantity of water is the quantity whichensures that any degradation of the organophosphite ligand proceeds bythe "non-catalytic mechanism" as described in "The Kinetic Rate Law forAutocatalytic Reactions" by Mata-Perez et al., Journal of ChemicalEducation, Vol. 64, No. 11, November 1987, pages 925 to 927, rather thanby the "catalytic mechanism" described in said article. Typicallymaximum water concentrations are only governed by practicalconsiderations. As noted, treatment conditions such as temperature,pressure and contact time may also vary greatly and any suitablecombination of such conditions may be employed herein. For instance, adecrease in one of such conditions may be compensated for by an increasein one or both of the other conditions, while the opposite correlationis also true. In general liquid temperatures ranging from about 10° C.to about 120° C., preferably from about 20° C. to about 80° C., and morepreferably from about 25° C. to about 60° C. should be suitable for mostinstances, although lower or higher temperatures could be employed ifdesired. As noted above, it has been surprisingly discovered thatminimum loss of organophosphite ligand occurs when a hydroformylationreaction product fluid containing a metal-organophosphite ligand complexcatalyst is contacted with water and the contacted water thereaftertreated with the ion exchange resins even at elevated temperatures.Normally the treatment is carried out under pressures ranging fromambient to reaction pressures and the contact time may vary from amatter of seconds or minutes to a few hours or more.

Moreover, success in removing phosphorus acidic compounds from thereaction product fluid according to the subject invention may bedetermined by measuring the rate degradation (consumption) of theorganophosphite ligand present in the hydroformylation reaction medium.The consumption rate can vary over a wide range, e.g., from about ≦0.6up to about 5 grams per liter per day, and will be governed by the bestcompromise between cost of ligand and treatment frequency to keephydrolysis below autocatalytic levels. Preferably the ion exchange andwater treatment of this invention is carried out in such a manner thatthe consumption of the desired organophosphite ligand present in thehydroformylation reaction medium of the hydroformylation process ismaintained at an acceptable rate, e.g., ≦0.5 grams of ligand per literper day, and more preferably ≦0.1 grams of ligand per liter per day, andmost preferably ≦0.06 grams of ligand per liter per day. As theneutralization and extraction of phosphorus acidic compounds into thewater proceeds, the pH of the water will decrease and become more andmore acidic. When the water reaches an unacceptable acidity level it maysimply be replaced with new water.

A preferred method of operation of this invention is to pass all or aportion of the reaction product fluid before aldehyde removal orreaction product fluid concentration after removal of aldehyde throughthe non-contacted water and the contacted water through one or more ionexchange resins. Alternately, water may be sprayed into or otherwiseadded to the at least one reaction zone or the at least one separationzone to achieve acidity control. The water layer formed may then beseparated, e.g., decanted, from the reaction product fluid and sent tothe one or more ion exchange resins. An advantage of this scheme is thatextraction capability is immediately available if acidity forms in thereaction product fluid. This invention is not intended to be limited inany manner by the permissible means for contacting a reaction productfluid with water or water with an ion exchange resin (either inside oroutside of the reaction zone, separation zone, scrubber zone or ionexchange zone).

For purposes of this invention, "non-contacted water" is contemplated toinclude water that has not been contacted with the reaction productfluid and "contacted water" is contemplated to include water that hasbeen contacted with the reaction product fluid and/or acid removalsubstances.

Any means to prepare the non-contacted water for use with the process ofthis invention can be used so long as the water is substantially free ofcatalyst poisons, inhibitors, or compounds that would promoteundesirable side reactions in the catalyst solution. A summary of watertreatment techniques can be found in the Kirk Othmer, Encyclopedia ofChemical Technology, Fourth Edition, 1996.

Water treatment should begin with an evaluation of the water qualityneeds for the process. For acid extraction from reaction product fluidscontaining metal-organophosphite ligand complex catalysts, the qualityof water required is generally of boiler quality or better. Sources ofwater for purification can vary greatly in purity from river watercontaining logs, silt and other debris, to steam condensate that isrelatively pure. If river water is to be used, purification starts withfiltration of the largest pieces. Grates or screens may be used for thisfirst filtration step. A number of techniques can be used to removeother solids that may be present in the water including; sedimentation,centrifugal separation, filtration, coagulation, flocculation, magneticseparation, or combinations of these. After clarified water is obtained,the remaining dissolved solids can also be treated in a number of ways.Distillation is still commonly practiced. Dissolved salts may be treatedwith other acids or bases to precipitate certain compounds. The acids orbases that are added are chosen based on the solubility of the compoundsthat will be produced. Ion exchange is another popular method forremoving dissolved salts. The most common ion exchange method usessodium as the cation. Other ion exchange techniques with protons orhydroxide ions may also be employed. Adsorption can be used to removesome metal salts and organic compounds that may be present. Activatedcarbon is used commonly as an adsorbent. Membranes are still anothertechnique that may be used removed dissolved salts or other colloidalparticles. Membranes separate based on size, electronic charge,hydrophobicity, or other physical-chemical property differences. Reverseosmosis is an example of using membranes to purify water. If dissolvedgases such as oxygen are present, the water can be stripped with steamor nitrogen or subjected to vacuum to remove or replace the dissolvedgas. A preferred process to purify non-contacted water necessary for theacid removal would be a combination of some of the aforementionedtechniques.

Internal techniques where additives are used to counteract the harmfuleffects of impurities can also be used to prepare non-contacted waterfor use in extraction, but the external techniques described in thepreceding paragraph are more preferred.

The contacted water employable in this invention may comprise anysuitable water such that the pH of the contacted water may range fromabout 2 to about 10, preferably from about 2.5 to about 9 and morepreferably from about 3 to about 8. The flowrate of water through theextractor and/or the addition of water to the at least one reaction zoneand/or the at least one separation zone should be sufficient to controlpH of the water at desired levels. An increased flowrate of waterthrough the extractor may cause removal, i.e., through the watereffluent, of certain amounts of one or more aldehyde products from theprocess.

In a preferred embodiment of this invention, one or more aldehydeproducts removed by water extraction can be recovered and returned tothe hydroformylation process as depicted in the process flow diagram ofFIG. 1. For example, the one or more aldehyde products may be returnedto the hydroformylation process by steam stripping the water effluentfrom the extractor and returning the organic phase of the condensedstripper heads to the hydroformylation process. The aqueous phase of thestripper heads may be returned to the stripper feed. The tails of thestripper may contain the acidic decomposition products from thecatalyst.

Said treatment of the water containing phosphorus acidic compoundsremoved from the reaction product fluid with the one or more ionexchange resins may be conducted in any suitable manner or fashiondesired that does not unduly adversely affect the basic hydroformylationprocess from which said reaction product fluid was derived. Forinstance, the ion exchange resin treatment may be conducted on all orany portion of the water that is to be treated and which has beenremoved from the at least one scrubber zone. The treated water may thenbe returned to the at least one scrubber zone. Alternately, water may besprayed into or otherwise added to the at least one reaction zone or theat least one separation zone to achieve acidity control. The water layerformed may then be separated, e.g., decanted, from the reaction productfluid and treated with one or more ion exchange resins to remove thephosphorus acidic compounds. The treated water may then be returned tothe at least one reaction zone or the at least one separation zone.

The manner in which the water containing phosphorus acidic compoundsremoved from the reaction product fluid and the one or more ion exchangeresins are contacted, as well as such treatment conditions, as theamount of water, the number and type of ion exchange resins,temperature, pressure and contact time are not narrowly critical andobviously need only be sufficient to obtain the results desired. Forinstance, said treatment may be carried out in any suitable vessel orcontainer which provides a suitable means for thorough contact betweenthe water and one or more ion exchange resins, may be employed herein.The amount of water and ion exchange resins employed by the subjectinvention and time of contact need only be that which is sufficient toremove at least some amount of the phosphorus acidic compounds whichcause hydrolytic degradation of the desirable organophosphite ligands.Preferably the amount of water and ion exchange resins is sufficient toat least maintain the concentration of such acidic compounds below thethreshold level that causes rapid degradation of the organophosphiteligand. Also, preferably, the fraction of water sent from the scrubberzone to the ion exchange zone may be controlled based on the pH of thewater in the scrubber zone.

As indicated above, the reaction product fluid may contain at least someamount of various phosphorus acidic compounds, for example, H₃ PO₃,aldehyde acid (hydroxyalkylphosphonic acid), H₃ PO₄, and the like, andother acidic compounds, for example, carboxylic acids such as butyricacid, and the like. If the one or more ion exchange resins should becomesaturated with carboxylic acids, the hydroformylation process of thisinvention can still be operated at desirably low levels of phosphorusacidic compounds. The stronger phosphorus acidic compounds are able todisplace the weaker carboxylic acids from the ion exchange resins in theoperation of this invention.

Anion exchange resins suitable for use in this invention include thewide variety of insoluble organic polymers obtained by additionpolymerization or polycondensation of suitable monomers and heretoforeused for preparing ion exchange resins. These organic polymers then aremodified subsequently, using techniques well-known to those skilled inthe art to provide the desired ion exchange capability. Insolubilizationof suitable polymers typically is achieved by chemical crosslinking, byradiation or by thermosetting. Examples of suitable polymers for the ionexchange resin are polystyrene, polyethylene, poly vinyl chloride,polyvinyl acetate, polyethylene imine and other polyalkylene imines,polyvinyl pyridine, polyacrylonitrile, polyacrylates, Saran®, Teflon®and the like. Suitable crosslinking agents for ensuring insolubility,particularly for polyolefins, are divinylbenzene, butadiene, diallylmaleate, diallyl phthalate, glycol dimethacrylate, and other di- ortriolefins.

Condensation polymers suitable for preparing the ion exchange resinsinclude phenol-formaldehyde resins, urea-formaldehyde resins, alkydresins (reaction products of polyhydric alcohols and polybasic acids),polyesters, such as Dacron® and polyamides. Also suitable arepolyamines, polyethers such as polyphenyl oxide, polystyrene oxide orpolypropylene oxide, polysulfides such as polyphenyl sulfide, andpolysulfones such as polyphenyl sulfone. Mixtures of copolymers also aresuitable. Celluloses also are included although they are not normallyconsidered resins. These resins are modified using techniques known tothose skilled in the ion exchange art, to provide the resin with its ionexchange capacity.

A particularly useful resin is a commercially available copolymer ofstyrene and divinylbenzene. Such resins are characterized by having longchains of polystyrene locked together by means of divinylbenzenecrosslinks into a three-dimensional, insoluble polymeric phase. However,in the broad practice of this invention, the particular resin used isnot critical.

Anion exchange resins are available in both the gellular andmacroreticular form. While both gellular and macroreticular forms of theresin can be used in this invention, it is preferred to usemacroreticular resins. Generally, macroreticular resins have asubstantially uniform macropore structure with average pore diametersabove about 50 μm. Gellular resins generally should be used only if thewater containing phosphorus acidic compounds removed from the reactionproduct fluid will cause the gellular resin to swell, which increasesthe available surface area of the resin, as recognized by those skilledin the ion exchange resin art.

Anion exchange resins are characterized as either strong base or weakbase anion exchange resins depending on the active ion exchange sites ofthe resin. Both strong base and weak base anion exchange resins can beused with this invention. Weak base anion exchange resins are preferredfor use in this invention. When using strong base anion exchange resinsin the practice of this invention, it is desirable to control thefraction of water flow to the ion exchange resin.

Strong base anion exchange resins consist of polymers having mobilemonovalent anions, such as hydroxide (OH⁻) and the like associated forexample with covalently bonded quaternary ammonium, phosphonium orarsonium functional groups or tertiary sulfonium functional groups.These functional groups are known as active sites and are distributedover the surface of the resin particle. Strong base anion exchangeresins have the capacity to undergo ion exchange independent of the pHof the medium by virtue of their intrinsic ionic character.Macroreticular strong base anion exchange resins in the hydroxide formare particularly preferred in the practice of this invention. Suchresins are commercially available from or can be readily prepared fromresins sold by Rohm and Haas Company under the registered trademarkAmberlyst®, e.g., Amberlyst® A-26 and Amberlyst® A-27. Other suitablestrong base anion exchange resins are commercially available from otherssuch as the Dow Chemical Company under the registered trademark DOWEX®21 K, 11 and MWA-I.

The resin matrix of weak base anion exchange resins contains chemicallybonded thereto a basic, nonionic functional group. The functional groupsinclude primary, secondary, or tertiary amine groups. Of these, tertiaryamine groups are preferred. These may be aliphatic, aromatic,heterocyclic or cycloalkane amine groups. They may also be diamine,triamine, or alkanolamine groups. The amines, for example, may includealpha, alpha'-dipyridyl, guanidine, and dicyanodiamidine groups. Othernitrogen-containing basic, non-ionic functional groups include nitrile,cyanate, isocyanate, thiocyanate, isothiocyanate, and isocyanide groups.Pyridine groups may also be employed. This invention is not, however,limited to any particular class of weak base anion exchange resins.

As weak base anion exchange resins, the aminated, styrenedivinylbenzenecopolymers, crosslinked with divinylbenzene to varying degrees in themolar range 1-40% of the monomer reacted, which also are commerciallyavailable from Rohm and Haas Company under the registered trademarkAmberlyst®, are particularly useful. These resins can be prepared, forexample, by the methods taught in U.S. Pat. No. 2,591,574. Amberlyst®A-21, crosslinked using divinylbenzene is a particularly useful resinfor this invention because of its porous, insoluble bead structure.Amberlyst® A-21 beads contain nitrogen in an amount of between about 4.2and about 4.8 milliequivalents per gram of resin, in the form oftertiary N,N-dimethylbenzylamine.

Weak base anion exchange resins are characterized by the fact that theypossess essentially no ion exchange properties at pH levels greater thanabout pH 7 as above this pH they contain no ionic groups. As indicatedabove, they are composed of polymers containing primary, secondary ortertiary amines, and the like. Further definition of strong and weakbase ion exchange resins, along with a discussion of their preparationand properties, are described in F. Helfferich "Ion Exchange", McGrawHill Book Co., New York, N.Y., 1962, pp. 16, 47-58, 78, 138-40, and in"Dowex-Ion Exchange", the Dow Chemical Co., Midland, Mich., 1958. Seealso U.S. Pat. No. 5,114,473, the disclosure of which is incorporatedherein be reference.

Additionally, liquid anion exchangers may also be used in thisinvention. These are typically fatty trialkylamines for the extractionof strong acids from aqueous media, e.g., Alamine® available from HenkelCorporation. Illustrative trialkylamines include, for example,trioctylamine, trilaurylamine, tri-isooctylamine, tri-isodecylamine, andtricaprylamine. Other liquid anion exchangers include atricaprylmethylammonium chloride, i.e., a liquid strong base anionexchanger, which in the conjugate carboxylate form would serve tosequester strong acids such as phosphoric, phosphorous, and phosphonicacids from aqueous media.

As noted above, the resin employed should be insoluble in the watercontaining phosphorus acidic compounds removed from the reaction productfluid. In the broad practice of this invention, by "insoluble" we meaninsoluble at temperatures below the decomposition temperature of theresin in the water.

The number of active ion exchange sites per unit mass or unit volume ofan ion exchange resin suitable for use in this invention may vary over awide range and is not critical. The quantity of active sites availableon a particular resin is quantified as the resin's "weight capacity",expressed as milliequivalents per gram. Generally, suitable resins willhave a weight capacity of above about 0.5 milliequivalents per gram andpreferably above about 1.0 milliequivalents per gram.

It should be noted that commercial grade ion exchange resin beads, suchas the Amberlyst® resins may be available in the halide, e.g., chloride,form or may contain halide impurities, e.g. chloride contaminates, whichare known to poison (adversely affect) metal-ligand complexhydroformylation catalysts. Thus, it is preferred in the case of ahydroformylation-related process that the ion exchange resin employableherein be at least substantially free of halogen contaminates and morepreferably essentially or entirely free from such halogen contaminates.Removal of such halogen contaminates, as well as any other undesirablecontaminates, from such ion exchange resins prior to their use may bereadily accomplished by conventional ion exchange and washing techniquesthat are well-known in the art. Ion exchange resins may also containresidual unsaturation which makes them inappropriate for the directtreatment of hydroformylation reaction product fluids containingmetal-organophosphite ligand complex catalysts, i.e., rhodiumprecipitation can occur on the resin surface and pores, thereby causingprocess complications.

The removal of phosphorus acidic compounds from water in accordance withthis invention can be accomplished simply by contacting the water withthe ion exchange resin. The quantity of ion exchange resin relative towater will depend upon the quantity of phosphorus acidic compounds inthe water. The quantity of ion exchange resin need only be sufficient toreduce the phosphorus acidic compound concentration to the desiredvalue. Based on a water standard having a phosphorus acidic compoundconcentration of about 10 parts per million, an amount, by volume, ofion exchange resin of about 10 milliliters of resin per liter of waterto be treated should be satisfactory for phosphorus acidic compoundremoval from the water.

The contact time between the ion exchange resin and the water containingphosphorus acidic compounds removed from the reaction product fluid needonly be sufficient to remove at least some of the phosphorus acidiccompounds from the water. The water containing phosphorus acidiccompounds can be contacted with the one or more ion exchange resins ineither a batch or continuous (or semi-continuous) mode. When operatingin a batch mode, the contact preferably involves agitation of a mixtureof the water containing phosphorus acidic compounds and the ion exchangeresin for about 0.01 to about 10 hours, more typically about 0.1 toabout 5 hours, followed by any known separation technique, e.g.,settling, centrifugation, filtration or the like. Preferably, theinvention is practiced in a continuous mode by flowing the watercontaining phosphorus acidic compounds through one or more containedbeds of the resin, e.g., a fixed bed, a moving bed or a fluidized bed,at a liquid flow rate ranging from about 0.1 to about 100 bed volumesper hour, more typically from about 1 to about 20 bed volumes per hour.The invention can employ any conventional apparatus designed for ionexchange service, special designs are not required. Obviously, adequatecontacting between the one or more ion exchange resins and the watercontaining phosphorus acidic compounds is important to obtain bestresults. As recognized by those skilled in this technology, the one ormore ion exchange resin beds are used to remove phosphorus acidiccompounds from the water until the level (concentration) of phosphorusacidic compounds in the treated water exiting the one or more resin bedsdecreases to a desired value.

The number of ion exchange resin beds which may be used in thisinvention is not narrowly critical. One or more ion exchange resin beds,e.g., a series of such beds, may be employed and any such bed may beeasily removed and/or replaced as required or desired.

In another embodiment, this invention relates to treating at least aportion of the hydroformylation reaction product fluid derived from saidhydroformylation process and which also contains phosphorus acidiccompounds formed during said hydroformylation process and/or thecontacted water which also contains phosphorus acidic compounds byintroducing one or more amines into the at least one scrubber orextraction zone sufficient to remove at least some amount of thephosphorus acidic compounds from said reaction product fluid and/or saidcontacted water. The amines should have substantial water solubility andare preferably tertiary amines. Illustrative amines include, e.g.,triethanolamine, N-methyl-di-ethanolamine, tris-(3-hydroxypropyl)-amine,and the like. The quantity of amines relative to reaction product fluidand/or contacted water will depend upon the quantity of phosphorusacidic compounds in the reaction product fluid and/or contacted water.The quantity of amines need only be sufficient to reduce the phosphorusacidic compound concentration to the desired value.

In a further embodiment, this invention relates to treating at least aportion of the hydroformylation reaction product fluid derived from saidhydroformylation process and which also contains phosphorus acidiccompounds formed during said hydroformylation process by introducing oneor more amines into the at least one reaction zone and/or the at leastone separation zone sufficient to remove at least some amount of thephosphorus acidic compounds from said reaction product fluid. The aminesshould have the following characteristics: (i) not reactive with thealdehyde product; (ii) not so basic as to promote aldol condensation;and (iii) amine salts are water soluble so as to facilitate removal fromthe reaction zone. Preferably, the amine salt is water soluble and isremoved through the aqueous phase in the reactor or more preferably, thehydroformylation reaction product fluid is put through the water/ionexchange treatment to remove acidity. Illustrative suitable aminesinclude those mentioned above. The quantity of amines relative toreaction product fluid will depend upon the quantity of phosphorusacidic compounds in the reaction product fluid. The quantity of aminesneed only be sufficient to reduce the phosphorus acidic compoundconcentration to the desired value.

In yet another embodiment, this invention relates to treating at least aportion of the hydroformylation reaction product fluid derived from saidhydroformylation process and which also contains phosphorus acidiccompounds formed during said hydroformylation process by introducing oneor more phosphines into the at least one reaction zone and/or the atleast one separation zone sufficient to remove at least some amount ofthe phosphorus acidic compounds from said reaction product fluid. Thephosphines should have sufficient stearic bulk to disfavor coordinationwith the metal-organopolyphosphite ligand complex catalyst. Thephosphines should be sufficiently basic to form salts with thephosphorus acid compounds. Salt removal may be facilitated since thesalts typically are soluble in water or the acidity can be transferredto water. Illustrative phosphines include, for example,cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine,tricyclohexylphosphine, tribenzylphosphine and the like. The quantity ofphosphines relative to reaction product fluid will depend upon thequantity of phosphorus acidic compounds in the reaction product fluid.The quantity of phosphines need only be sufficient to reduce thephosphorus acidic compound concentration to the desired value.

Illustrative of suitable ion exchange resins, amines and phosphinesinclude those permissible ion exchange resins, amines and phosphinesdescribed in Kirk-Othmer, Encyclopedia of Chemical Technology, FourthEdition, 1996, the pertinent portions of which are incorporated hereinby reference.

Optionally, an organic nitrogen compound may be added to thehydroformylation reaction product fluid to scavenge the acidichydrolysis byproducts formed upon hydrolysis of the organophosphiteligand, as taught, for example, in U.S. Pat. No. 4,567,306. Such organicnitrogen compounds may be used to react with and to neutralize theacidic compounds by forming conversion product salts therewith, therebypreventing the rhodium from complexing with the acidic hydrolysisbyproducts and thus helping to protect the activity of the metal, e.g.,rhodium, catalyst while it is present in the reaction zone underhydroformylation conditions. The choice of the organic nitrogen compoundfor this function is, in part, dictated by the desirability of using abasic material that is soluble in the reaction medium and does not tendto catalyze the formation of aldols and other condensation products at asignificant rate or to unduly react with the product aldehyde.

Such organic nitrogen compounds may contain from 2 to 30 carbon atoms,and preferably from 2 to 24 carbon atoms. Primary amines should beexcluded from use as said organic nitrogen compounds. Preferred organicnitrogen compounds should have a distribution coefficient that favorssolubility in the organic phase. In general more preferred organicnitrogen compounds useful for scavenging the phosphorus acidic compoundspresent in the hydroformylation reaction product fluid of this inventioninclude those having a pKa value within ±3 of the pH of the contactedwater employed. Most preferably the pKa value of the organic nitrogencompound will be essentially about the same as the pH of the wateremployed. Of course it is to be understood that while it may bepreferred to employ only one such organic nitrogen compound at a time inany given hydroformylation process, if desired, mixtures of two or moredifferent organic nitrogen compounds may also be employed in any givenprocesses.

Illustrative organic nitrogen compounds include e.g., trialkylamines,such as triethylamine, tri-n-propylamine, tri-n-butylamine,tri-iso-butylamine, tri-iso-propylamine, tri-n-hexylamine,tri-n-octylamine, dimethyl-iso-propylamine, dimethyl-hexadecylamine,methyl-di-n-octylamine, and the like, as well as substituted derivativesthereof containing one or more noninterfering substituents such ashydroxy groups, for example triethanolamine, N-methyl-di-ethanolamine,tris-(3-hydroxypropyl)-amine, and the like. Heterocyclic amines can alsobe used such as pyridine, picolines, lutidines, collidines,N-methylpiperidine, N-methylmorpholine, N-2'-hydroxyethylmorpholine,quinoline, iso-quinoline, quinoxaline, acridien, quinuclidine, as wellas, diazoles, triazole, diazine and triazine compounds, and the like.Also suitable for possible use are aromatic tertiary amines, such asN,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine,N-methyldiphenylamine, N,N-dimethylbenzylamine,N,N-dimethyl-1-naphthylamine, and the like. Compounds containing two ormore amino groups, such as N,N,N',N'-tetramethylethylene diamine andtriethylene diamine (i.e. 1,4-diazabicyclo- 2,2,2!-octane) can also bementioned.

Preferred organic nitrogen compounds useful for scavenging thephosphorus acidic compounds present in the hydroformylation reactionproduct fluids of the this invention are heterocyclic compounds selectedfrom the group consisting of diazoles, triazoles, diazines andtriazines, such as those disclosed and employed in copending U.S. patentapplication Ser. No. 08/756,789, filed on an even date herewith, thedisclosure of which is incorporated herein by reference. For example,benzimidazole and benztriazole are preferred candidates for such use.

Illustrative of suitable organic nitrogen compounds include thosepermissible organic nitrogen compounds described in Kirk-Othmer,Encyclopedia of Chemical Technology, Fourth Edition, 1996, the pertinentportions of which are incorporated herein by reference.

The amount of organic nitrogen compound that may be present in thereaction product fluid for scavenging the phosphorus acidic compoundspresent in the hydroformylation reaction product fluids of the thisinvention is typically sufficient to provide a concentration of at leastabout 0.0001 moles of free organic nitrogen compound per liter ofreaction product fluid. In general the ratio of organic nitrogencompound to total organophosphite ligand (whether bound with rhodium orpresent as free organophosphite) is at least about 0.1:1 and even morepreferably at least about 0.5:1. The upper limit on the amount oforganic nitrogen compound employed is governed mainly only by economicalconsiderations. Organic nitrogen compound:organophosphite molar ratiosof at least about 1:1 up to about 5:1 should be sufficient for mostpurpose.

It is to be understood the organic nitrogen compound employed toscavenge said phosphorus acidic compounds need not be the same as theheterocyclic nitrogen compound employed to protect the metal catalystunder harsh conditions such as exist in the aldehydevaporizer-separator, as taught in copending U.S. patent application Ser.No. 08/756,789, referred to above. However, if said organic nitrogencompound and said heterocyclic nitrogen compound are desired to be thesame and perform both said functions in a given process, care should betaken to see that there will be a sufficient amount of the heterocyclicnitrogen compound present in the reaction medium to also provide thatamount of free heterocyclic nitrogen compound in the hydroformylationprocess, e.g., vaporizer-separator, that will allow both desiredfunctions to be achieved.

Accordingly the water extraction of this invention will not only removefree phosphoric acidic compounds from the metal-organophosphite ligandcomplex catalyst containing reaction product fluids, the water alsosurprisingly removes the phosphorus acidic material of the conversionproduct salt formed by the use of the organic nitrogen compoundscavenger when employed, i.e., the phosphorus acid of said conversionproduct salt remains behind in the water, while the treated reactionproduct fluid, along with the reactivated (free) organic nitrogencompound is returned to the hydroformylation reaction zone.

Another problem that has been observed when organopolyphosphite ligandpromoted metal catalysts are employed in hydroformylation processes,e.g., continuous liquid catalyst recycle hydroformylation processes,that involve harsh conditions such as recovery of the aldehyde via avaporizer-separator, i.e., the slow loss in catalytic activity of thecatalysts is believed due at least in part to the harsh conditions suchas exist in a vaporizer employed in the separation and recovery of thealdehyde product from its reaction product fluid. For instance, it hasbeen found that when an organopolyphosphite promoted rhodium catalyst isplaced under harsh conditions such as high temperature and low carbonmonoxide partial pressure, that the catalyst deactivates at anaccelerated pace with time, due most likely to the formation of aninactive or less active rhodium species, which may also be susceptibleto precipitation under prolonged exposure to such harsh conditions. Suchevidence is also consistent with the view that the active catalyst whichunder hydroformylation conditions is believed to comprise a complex ofrhodium, organopolyphosphite, carbon monoxide and hydrogen, loses atleast some of its coordinated carbon monoxide ligand during exposure tosuch harsh conditions as encountered in vaporization, which provides aroute for the formation of catalytically inactive or less active rhodiumspecies. The means for preventing or minimizing such catalystdeactivation and/or precipitation involves carrying out the inventiondescribed and taught in copending U.S. patent application Ser. No.08/756,789, referred to above, which comprises carrying out thehydroformylation process under conditions of low carbon monoxide partialpressure in the presence of a free heterocyclic nitrogen compound asdisclosed therein.

By way of further explanation it is believed the free heterocyclicnitrogen compound serves as a replacement ligand for the lost carbonmonoxide ligand thereby forming a neutral intermediate metal speciescomprising a complex of the metal, organopolyphosphite, the heterocyclicnitrogen compound and hydrogen during such harsh conditions, e.g.,vaporization separation, thereby preventing or minimizing the formationof any such above mentioned catalytic inactive or less active metalspecies. It is further theorized that the maintenance of catalyticactivity, or the minimization of its deactivation, throughout the courseof such continuous liquid recycle hydroformylation is due toregeneration of the active catalyst from said neutral intermediate metalspecies in the reactor (i.e. hydroformylation reaction zone) of theparticular hydroformylation process involved. It is believed that underthe higher syn gas pressure hydroformylation conditions in the reactor,the active catalyst complex comprising metal, e.g., rhodium,organopolyphosphite, carbon monoxide and hydrogen is regenerated as aresult of some of the carbon monoxide in the reactant syn gas replacingthe heterocyclic nitrogen ligand of the recycled neutral intermediaterhodium species. That is to say, carbon monoxide having a strongerligand affinity for rhodium, replaces the more weakly bondedheterocyclic nitrogen ligand of the recycled neutral intermediaterhodium species that was formed during vaporization separation asmentioned above, thereby reforming the active catalyst in thehydroformylation reaction zone.

Thus the possibility of metal catalyst deactivation due to such harshconditions is said to be minimized or prevented by carrying out suchdistillation of the desired aldehyde product from themetal-organopolyphosphite catalyst containing reaction product fluids inthe added presence of a free heterocyclic nitrogen compound having afive or six membered heterocyclic ring consisting of 2 to 5 carbon atomsand from 2 to 3 nitrogen atoms, at least one of said nitrogen atomscontaining a double bond. Such free heterocyclic nitrogen compounds maybe selected from the class consisting of diazole, triazole, diazine, andtriazine compounds, such as, e.g., benzimidazole or benzotriazole, andthe like. The term "free" as it applies to said heterocyclic nitrogencompounds is employed therein to exclude any acid salts of suchheterocyclic nitrogen compounds, i.e., salt compounds formed by thereaction of any phosphorus acidic compound present in thehydroformylation reaction product fluids with such free heterocyclicnitrogen compounds as discussed herein above.

It is to be understood that while it may be preferred to employ only onefree heterocyclic nitrogen compound at a time in any givenhydroformylation process, if desired, mixtures of two or more differentfree heterocyclic nitrogen compounds may also be employed in any givenprocess. Moreover the amount of such free heterocyclic nitrogencompounds present during harsh conditions, e.g., the vaporizationprocedure, need only be that minimum amount necessary to furnish thebasis for at least some minimization of such catalyst deactivation asmight be found to occur as a result of carrying out an identical metalcatalyzed liquid recycle hydroformylation process under essentially thesame conditions, in the absence of any free heterocyclic nitrogencompound during vaporization separation of the aldehyde product. Amountsof such free heterocyclic nitrogen compounds ranging from about 0.01 upto about 10 weight percent, or higher if desired, based on the totalweight of the hydroformylation reaction product fluid to be distilledshould be sufficient for most purposes.

An alternate method of transferring acidity from the hydroformylationreaction product fluid to an aqueous fraction is through theintermediate use of a heterocyclic amine which has a fluorocarbon orsilicone side chain of sufficient size that it is immiscible in both thehydroformylation reaction product fluid and in the aqueous fraction. Theheterocyclic amine may first be contacted with the hydroformylationreaction product fluid where the acidity present in the reaction productfluid will be transferred to the nitrogen of the heterocyclic amine.This heterocyclic amine layer may then be decanted or otherwiseseparated from the reaction product fluid before contacting it with theaqueous fraction where it again would exist as a separate phase. Theheterocyclic amine layer may then be returned to contact thehydroformylation reaction product fluid.

The hydroformylation processes of this invention may be carried outusing, for example, a fixed bed reactor, a fluid bed reactor, acontinuous stirred tank reactor (CSTR) or a slurry reactor. The optimumsize and shape of the catalysts will depend on the type of reactor used.In general, for fluid bed reactors, a small, spherical catalyst particleis preferred for easy fluidization. With fixed bed reactors, largercatalyst particles are preferred so the back pressure within the reactoris kept reasonably low. The at least one reaction zone employed in thisinvention may be a single vessel or may comprise two or more discretevessels. The at least one separation zone employed in this invention maybe a single vessel or may comprise two or more discrete vessels. The atleast one scrubber zone employed in this invention may be a singlevessel or may comprise two or more discrete vessels. The at least oneion exchange zone employed in this invention may be a single vessel ormay comprise two or more discrete vessels. It should be understood thatthe reaction zone(s) and separation zone(s) employed herein may exist inthe same vessel or in different vessels. For example, reactiveseparation techniques such as reactive distillation, reactive membraneseparation and the like may occur in the reaction zone(s).

The hydroformylation processes of this invention can be conducted in abatch or continuous fashion, with recycle of unconsumed startingmaterials if required. The reaction can be conducted in a singlereaction zone or in a plurality of reaction zones, in series or inparallel or it may be conducted batchwise or continuously in anelongated tubular zone or series of such zones. The materials ofconstruction employed should be inert to the starting materials duringthe reaction and the fabrication of the equipment should be able towithstand the reaction temperatures and pressures. Means to introduceand/or adjust the quantity of starting materials or ingredientsintroduced batchwise or continuously into the reaction zone during thecourse of the reaction can be conveniently utilized in the processesespecially to maintain the desired molar ratio of the startingmaterials. The reaction steps may be effected by the incrementaladdition of one of the starting materials to the other. Also, thereaction steps can be combined by the joint addition of the startingmaterials. When complete conversion is not desired or not obtainable,the starting materials can be separated from the product, for example bydistillation, and the starting materials then recycled back into thereaction zone.

The hydroformylation processes may be conducted in either glass lined,stainless steel or similar type reaction equipment. The reaction zonemay be fitted with one or more internal and/or external heatexchanger(s) in order to control undue temperature fluctuations, or toprevent any possible "runaway" reaction temperatures.

The hydroformylation processes of this invention may be conducted in oneor more steps or stages. The exact number of reaction steps or stageswill be governed by the best compromise between capital costs andachieving high catalyst selectivity, activity, lifetime and ease ofoperability, as well as the intrinsic reactivity of the startingmaterials in question and the stability of the starting materials andthe desired reaction product to the reaction conditions.

In an embodiment, the hydroformylation processes useful in thisinvention may be carried out in a multistaged reactor such as described,for example, in copending U.S. patent application Ser. No. 08/757,743,filed on an even date herewith, the disclosure of which is incorporatedherein by reference. Such multistaged reactors can be designed withinternal, physical barriers that create more than one theoreticalreactive stage per vessel. In effect, it is like having a number ofreactors inside a single continuous stirred tank reactor vessel.Multiple reactive stages within a single vessel is a cost effective wayof using the reactor vessel volume. It significantly reduces the numberof vessels that otherwise would be required to achieve the same results.Fewer vessels reduces the overall capital required and maintenanceconcerns with separate vessels and agitators.

For purposes of this invention, the term "hydrocarbon" is contemplatedto include all permissible compounds having at least one hydrogen andone carbon atom. Such permissible compounds may also have one or moreheteroatoms. In a broad aspect, the permissible hydrocarbons includeacyclic (with or without heteroatoms) and cyclic, branched andunbranched, carbocyclic and heterocyclic, aromatic and nonaromaticorganic compounds which can be substituted or unsubstituted.

As used herein, the term "substituted" is contemplated to include allpermissible substituents of organic compounds unless otherwiseindicated. In a broad aspect, the permissible substituents includeacyclic and cyclic, branched and unbranched, carbocyclic andheterocyclic, aromatic and nonaromatic substituents of organiccompounds. Illustrative substituents include, for example, alkyl,alkyloxy, aryl, aryloxy, hydroxy, hydroxyalkyl, amino, aminoalkyl,halogen and the like in which the number of carbons can range from 1 toabout 20 or more, preferably from 1 to about 12. The permissiblesubstituents can be one or more and the same or different forappropriate organic compounds. This invention is not intended to belimited in any manner by the permissible substituents of organiccompounds.

Certain of the following examples are provided to further illustratethis invention.

EXAMPLE 1

Amberlyst® A-21 resin was charged to a stainless steel vessel. Asolution of 180 parts per million hydroxy amyl phosphonic acid waspumped through the bed at a rate of 0.31 (grams acid solution)/(grams ofresin)/hour. The concentration of hydroxy amyl phosphonic acid in theexit solution was very low (2 to 3 parts per million), and the pH of theexit solution was typically 9. Free amines were suspected of beingrinsed from the resin causing the pH to be higher than 7. This resin wasregenerated with 4 percent sodium hydroxide solution according to themanufacturer's instructions. Pure water was then passed though the bedand associated tubing until the exit pH was below 8. Approximately 250to 300 times as much water as resin volume was required. The 180 partsper million hydroxy amyl phosphonic acid was again pumped through theresin in an up-flow configuration at a rate of 0.31 (grams acidsolution)/(grams of resin)/hour. This rate was held for 71/2 days withthe pH of the effluent of 7.1±0.2. The pH of the inlet acid solution was3.2±0.1. At the end of 71/2 days the flowrate of the acid was increasedto 0.94 (grams acid solution)/(grams of resin)/hour. After 1 day, the pHof the exit solution dropped to 6.7. After 4 days the pH was 6.5.

EXAMPLE 2

This control example illustrates the stability of Ligand F (asidentified herein) in a solution containing 200 parts per million ofrhodium, and 0.39 percent by weight of Ligand F in butyraldehydecontaining aldehyde dimer and trimer in the absence of added acid orbenzimidazole.

To a clean, dry 25 milliliter vial was added 12 grams of thebutyraldehyde solution mentioned above. Samples were analyzed for LigandF using High Performance Liquid Chromatography after 24 and 72 hours.The weight percent of Ligand F was determined by High Performance LiquidChromatography relative to a calibration curve. No change in theconcentration of Ligand F was observed after either 24 or 72 hours.

EXAMPLE 3

This Example is similar to Example 2 except that phosphorus acid wasadded to simulate the type of acid that might be formed duringhydrolysis of an organophosphite.

The procedure for Example 2 was repeated with the modification of adding0.017 grams of phosphorous acid (H₃ PO₃) to the 12 gram solution. After24 hours the concentration of Ligand F had decreased from 0.39 to 0.12percent by weight; after 72 hours the concentration of Ligand F haddecreased to 0.04 percent by weight. This data shows that strong acidscatalyze the decomposition of Ligand F.

EXAMPLE 4

This Example is similar to Example 2 except that both phosphorus acidand benzimidazole were added.

The procedure for Example 2 was repeated with the modification of adding0.018 grams of phosphorous acid and 0.0337 grams of benzimidazole to thesolution. No decomposition of Ligand F was observed after either 24 or72 hours. This shows that the addition of benzimidazole effectivelybuffers the effect of the strong acid and thereby prevents the rapiddecomposition of Ligand F.

EXAMPLE 5

The following series of experiments were performed in order to determinethe relationship of the pKa of a base to the effectiveness of the baseto remain in the organic phase upon contact with an equimolar aqueousacid solution. In all cases the experiments were performed undernitrogen, unless otherwise specified.

Solutions were prepared by dissolving a quantity of acid or base insolvent so that the final concentration was equal to 0.1 moles/liter.The 1×10⁻³ moles/liter solutions were prepared by taking an aliquot ofthe 0.1 moles/liter solution and diluting to the specifiedconcentration. The 1×10⁻⁵ moles/liter solutions were prepared in thesame manner as the 1×10⁻³ moles/liter solution with the modification ofusing an aliquot of the 1×10⁻³ moles/liter solution in place of the 0.1moles/liter solution.

In each extraction experiment, 5 milliliters of base solution inbutyraldehyde was added to a clean, dry vial. To this vial was added 5milliliters of equimolar H₃ PO₃ solution. The resulting mixture wasrapidly shaken for several minutes and then allowed to phase separate. A1 milliliter aliquot of the aqueous layer was then transferred to aclean, dry vial. To this vial was added 1 milliliter of pH 7sodium/potassium phosphate buffer and 0.1 milliliter of Tergitol® 15-S-9surfactant. The solution was shaken vigorously, and an aliquot wasanalyzed by high performance liquid chromatography for base content. Theamount of base was then compared with a dichloromethane solution at theinitial concentration. The partition coefficients calculated are forpartitioning of the base from the organic phase to the water phase andis defined as K=amount of base in the water phase/amount of base in theorganic phase. The results of the extraction experiment are summarizedin Table A.

                                      TABLE A                                     __________________________________________________________________________               pKa                                                                           of Concentration                                                                             Concentration                                       Run                                                                              Base    base                                                                             (moles/liter)                                                                        Acid (moles/liter)                                                                        K                                            __________________________________________________________________________    1  2-benzylpyridine                                                                      5.1                                                                              1 × 10.sup.-3                                                                  H.sub.3 PO.sub.3                                                                   1 × 10.sup.-3                                                                  0.22                                         2  2-benzylpyridine                                                                      5.1                                                                              1 × 10.sup.-5                                                                  H.sub.3 PO.sub.3                                                                   1 × 10.sup.-5                                                                  0.30                                         3  quinoline                                                                             4.8                                                                              1 × 10.sup.-3                                                                  H.sub.3 PO.sub.3                                                                   1 × 10.sup.-3                                                                  0.43                                         4  quinoline                                                                             4.8                                                                              1 × 10.sup.-5                                                                  H.sub.3 PO.sub.3                                                                   1 × 10.sup.-5                                                                  1.20                                         5  3-acetylpyridine                                                                      3.3                                                                              1 × 10.sup.-3                                                                  H.sub.3 PO.sub.3                                                                   1 × 10.sup.-3                                                                  0.93                                         6  3-acetylpyridine                                                                      3.3                                                                              1 × 10.sup.-5                                                                  H.sub.3 PO.sub.3                                                                   1 × 10.sup.-5                                                                  0.00                                         7  benzotriazole                                                                         1.6                                                                              1 × 10.sup.-3                                                                  H.sub.3 PO.sub.3                                                                   1 × 10.sup.-3                                                                  0.08                                         8  benzotriazole                                                                         1.6                                                                              1 × 10.sup.-5                                                                  H.sub.3 PO.sub.3                                                                   1 × 10.sup.-5                                                                  0.00                                         9  1-benzyl-2-                                                                           -0.7                                                                             1 × 10.sup.-3                                                                  H.sub.3 PO.sub.3                                                                   1 × 10.sup.-3                                                                  0.02                                            pyrrolidinone                                                              10 1-benzyl-2-                                                                           -0.7                                                                             1 × 10.sup.-5                                                                  H.sub.3 PO.sub.3                                                                   1 × 10.sup.-5                                                                  0.00                                            pyrrolidinone                                                              __________________________________________________________________________

The results show that the smaller the pKa of the base, the more baseremains in the organic phase.

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

We claim:
 1. A process for separating one or more phosphorus acidiccompounds from a hydroformylation reaction product fluid containing saidone or more phosphorus acidic compounds, a metal-organophosphite ligandcomplex catalyst and optionally free organophosphite ligand whichprocess comprises (a) treating said hydroformylation reaction productfluid with water sufficient to remove at least some amount of said oneor more phosphorus acidic compounds from said hydroformylation reactionproduct fluid and (b) treating the water which contains phosphorusacidic compounds removed from said hydroformylation reaction productfluid with an ion exchange resin sufficient to remove at least someamount of said one or more phosphorus acidic compounds from said water.2. A process for stabilizing an organophosphite ligand againsthydrolytic degradation and/or a metal-organophosphite ligand complexcatalyst against deactivation which process comprises (a) treating ahydroformylation reaction product fluid containing ametal-organophosphite ligand complex catalyst and optionally freeorganophosphite ligand and which also contains one or more phosphorusacidic compounds, with water sufficient to remove at least some amountof said one or more phosphorus acidic compounds from saidhydroformylation reaction product fluid and (b) treating the water whichcontains phosphorus acidic compounds removed from said hydroformylationreaction product fluid with an ion exchange resin sufficient to removeat least some amount of said one or more phosphorus acidic compoundsfrom said water.
 3. A process for preventing and/or lessening hydrolyticdegradation of an organophosphite ligand and/or deactivation of ametal-organophosphite ligand complex catalyst which process comprises(a) treating a hydroformylation reaction product fluid containing ametal-organophosphite ligand complex catalyst and optionally freeorganophosphite ligand and which also contains one or more phosphorusacidic compounds, with water sufficient to remove at least some amountof said one or more phosphorus acidic compounds from saidhydroformylation reaction product fluid and (b) treating the water whichcontains phosphorus acidic compounds removed from said hydroformylationreaction product fluid with an ion exchange resin sufficient to removeat least some amount of said one or more phosphorus acidic compoundsfrom said water.
 4. An improved hydroformylation process for producingone or more aldehydes which comprises (i) reacting in at least onereaction zone one or more olefinic unsaturated compounds with carbonmonoxide and hydrogen in the presence of a metal-organophosphite ligandcomplex catalyst and optionally free organophosphite ligand to produce areaction product fluid comprising one or more aldehydes and (ii)separating in at least one separation zone or in said at least onereaction zone the one or more aldehydes from said reaction productfluid, the improvement comprising preventing and/or lessening hydrolyticdegradation of any said organophosphite ligand and deactivation of saidmetal-organophosphite ligand complex catalyst by (a) treating in atleast one scrubber zone at least a portion of said reaction productfluid derived from said hydroformylation process and which also containsphosphorus acidic compounds formed during said hydroformylation processwith water sufficient to remove at least some amount of the phosphorusacidic compounds from said reaction product fluid and (b) treating in atleast one ion exchange zone at least a portion of the water whichcontains phosphorus acidic compounds removed from said reaction productfluid with one or more ion exchange resins sufficient to remove at leastsome amount of the phosphorus acidic compounds from said water.
 5. Theimproved hydroformylation process of claim 4 which comprises (i)reacting in at least one reaction zone one or more olefinic unsaturatedcompounds with carbon monoxide and hydrogen in the presence of ametal-organophosphite ligand complex catalyst and optionally freeorganophosphite ligand to produce a reaction product fluid comprisingone or more aldehydes and (ii) separating in at least one separationzone or in said at least one reaction zone the one or more aldehydesfrom said reaction product fluid, the improvement comprising preventingand/or lessening hydrolytic degradation of any said organophosphiteligand and deactivation of said metal-organophosphite ligand complexcatalyst by (a) treating in at least one scrubber zone at least aportion of said reaction product fluid derived from saidhydroformylation process and which also contains phosphorus acidiccompounds formed during said hydroformylation process with watersufficient to remove at least some amount of the phosphorus acidiccompounds from said reaction product fluid, (b) returning the treatedreaction product fluid to said at least one reaction zone or said atleast one separation zone, (c) treating in at least one ion exchangezone at least a portion of the water which contains phosphorus acidiccompounds removed from said reaction product fluid with one or more ionexchange resins sufficient to remove at least some amount of thephosphorus acidic compounds from said water, and (d) returning thetreated water to said at least one scrubber zone.
 6. The improvedhydroformylation process of claim 4 which comprises (i) reacting in atleast one reaction zone one or more olefinic unsaturated compounds withcarbon monoxide and hydrogen in the presence of a metal-organophosphiteligand complex catalyst and optionally free organophosphite ligand toproduce a reaction product fluid comprising one or more aldehydes and(ii) separating in at least one separation zone or in said at least onereaction zone the one or more aldehydes from said reaction productfluid, the improvement comprising preventing and/or lessening hydrolyticdegradation of any said organophosphite ligand and deactivation of saidmetal-organophosphite ligand complex catalyst by (a) withdrawing fromsaid at least one reaction zone or said at least one separation zone atleast a portion of a reaction product fluid derived from saidhydroformylation process and which also contains phosphorus acidiccompounds formed during said hydroformylation process, (b) treating inat least one scrubber zone at least a portion of the withdrawn reactionproduct fluid derived from said hydroformylation process and which alsocontains phosphorus acidic compounds formed during said hydroformylationprocess with water sufficient to remove at least some amount of thephosphorus acidic compounds from said reaction product fluid, (c)returning the treated reaction product fluid to said at least onereaction zone or said at least one separation zone, (d) withdrawing fromsaid at least one scrubber zone at least a portion of said water whichcontains phosphorus acidic compounds removed from said reaction productfluid, (e) treating in at least one ion exchange zone at least a portionof the withdrawn water which contains phosphorus acidic compoundsremoved from said reaction product fluid with one or more ion exchangeresins sufficient to remove at least some amount of the phosphorusacidic compounds from said water, (f) returning the treated water tosaid at least one scrubber zone, and (g) optionally regenerating saidone or more ion exchange resins.
 7. The improved hydroformylationprocess of claim 4 which comprises (i) reacting in at least one reactionzone one or more olefinic unsaturated compounds with carbon monoxide andhydrogen in the presence of a metal-organophosphite ligand complexcatalyst and optionally free organophosphite ligand to produce areaction product fluid comprising one or more aldehydes and (ii)separating in at least one separation zone or in said at least onereaction zone the one or more aldehydes from said reaction productfluid, the improvement comprising preventing and/or lessening hydrolyticdegradation of any said organophosphite ligand and deactivation of saidmetal-organophosphite ligand complex catalyst by (a) treating at least aportion of said reaction product fluid derived from saidhydroformylation process and which also contains phosphorus acidiccompounds formed during said hydroformylation process by introducingwater into said at least one reaction zone and/or said at least oneseparation zone sufficient to remove at least some amount of thephosphorus acidic compounds from said reaction product fluid and (b)treating in at least one ion exchange zone at least a portion of thewater which contains phosphorus acidic compounds removed from saidreaction product fluid with one or more ion exchange resins sufficientto remove at least some amount of the phosphorus acidic compounds fromsaid water.
 8. The improved hydroformylation process of claim 4 whichcomprises (i) reacting in at least one reaction zone one or moreolefinic unsaturated compounds with carbon monoxide and hydrogen in thepresence of a metal-organophosphite ligand complex catalyst andoptionally free organophosphite ligand to produce a reaction productfluid comprising one or more aldehydes and (ii) separating in at leastone separation zone or in said at least one reaction zone the one ormore aldehydes from said reaction product fluid, the improvementcomprising preventing and/or lessening hydrolytic degradation of anysaid organophosphite ligand and deactivation of saidmetal-organophosphite ligand complex catalyst by (a) withdrawing fromsaid at least one reaction zone or said at least one separation zone atleast a portion of a reaction product fluid derived from saidhydroformylation process and which also contains phosphorus acidiccompounds formed during said hydroformylation process, (b) treating inat least one scrubber zone at least a portion of the withdrawn reactionproduct fluid derived from said hydroformylation process and which alsocontains phosphorus acidic compounds formed during said hydroformylationprocess with water sufficient to remove at least some amount of thephosphorus acidic compounds from said reaction product fluid, (c)returning the treated reaction product fluid to said at least onereaction zone or said at least one separation zone, (d) treating in saidat least one scrubber zone at least a portion of the withdrawn waterwhich contains phosphorus acidic compounds removed from said reactionproduct fluid with one or more ion exchange resins sufficient to removeat least some amount of the phosphorus acidic compounds from said water,and (e) optionally regenerating said one or more ion exchange resins. 9.An improved hydroformylation process for producing aldehydes whichcomprises (i) reacting in at least one reaction zone one or moreolefinic unsaturated compounds with carbon monoxide and hydrogen in thepresence of a metal-organophosphite ligand complex catalyst andoptionally free organophosphite ligand to produce a reaction productfluid comprising one or more aldehydes and (ii) separating in at leastone separation zone or in said at least one reaction zone the one ormore aldehydes from said reaction product fluid, the improvementcomprising preventing and/or lessening hydrolytic degradation of anysaid organophosphite ligand and deactivation of saidmetal-organophosphite ligand complex catalyst by (a) withdrawing fromsaid at least one reaction zone or said at least one separation zone atleast a portion of a reaction product fluid derived from saidhydroformylation process and which also contains phosphorus acidiccompounds formed during said hydroformylation process, (b) treating inat least one scrubber zone at least a portion of the withdrawn reactionproduct fluid derived from said hydroformylation process and which alsocontains phosphorus acidic compounds formed during said hydroformylationprocess with water sufficient to remove at least some amount of thephosphorus acidic compounds from said reaction product fluid, (c)returning the treated reaction product fluid to said at least onereaction zone or said at least one separation zone, (d) treating in saidat least one scrubber zone at least a portion of the withdrawn waterwhich contains phosphorus acidic compounds removed from said reactionproduct fluid with one or more amines sufficient to remove at least someamount of the phosphorus acidic compounds from said water, and (e)optionally replacing said one or more amines.
 10. An improvedhydroformylation process for producing one or more aldehydes whichcomprises (i) reacting in at least one reaction zone one or moreolefinic unsaturated compounds with carbon monoxide and hydrogen in thepresence of a metal-organophosphite ligand complex catalyst andoptionally free organophosphite ligand to produce a reaction productfluid comprising one or more aldehydes and (ii) separating in at leastone separation zone or in said at least one reaction zone the one ormore aldehydes from said reaction product fluid, the improvementcomprising preventing and/or lessening hydrolytic degradation of anysaid organophosphite ligand and deactivation of saidmetal-organophosphite ligand complex catalyst by treating at least aportion of said reaction product fluid derived from saidhydroformylation process and which also contains phosphorus acidiccompounds formed during said hydroformylation process by introducing oneor more amines into said at least one reaction zone and/or said at leastone separation zone sufficient to remove at least some amount of thephosphorus acidic compounds from said reaction product fluid.
 11. Animproved hydroformylation process for producing one or more aldehydeswhich comprises (i) reacting in at least one reaction zone one or moreolefinic unsaturated compounds with carbon monoxide and hydrogen in thepresence of a metal-organophosphite ligand complex catalyst andoptionally free organophosphite ligand to produce a reaction productfluid comprising one or more aldehydes and (ii) separating in at leastone separation zone or in said at least one reaction zone the one ormore aldehydes from said reaction product fluid, the improvementcomprising preventing and/or lessening hydrolytic degradation of anysaid organophosphite ligand and deactivation of saidmetal-organophosphite ligand complex catalyst by treating at least aportion of said reaction product fluid derived from saidhydroformylation process and which also contains phosphorus acidiccompounds formed during said hydroformylation process by introducing oneor more phosphines into said at least one reaction zone and/or said atleast one separation zone sufficient to remove at least some amount ofthe phosphorus acidic compounds from said reaction product fluid. 12.The process of claim 1 wherein the ion exchange resin comprises a strongbase anion exchange resin or a weak base anion exchange resin.
 13. Theprocess of claim 4 wherein said hydroformylation process comprises acontinuous liquid recycle process.
 14. The process of claim 4 whereinsaid metal-organophosphite ligand complex catalyst is homogeneous orheterogeneous.
 15. The process of claim 4 wherein said reaction productfluid contains a homogeneous or heterogeneous metal-organophosphiteligand complex catalyst or at least a portion of said reaction productfluid contacts a fixed heterogeneous metal-organophosphite ligandcomplex catalyst during said hydroformylation process.
 16. The processof claim 4 wherein said separating of one or more aldehydes from thereaction product fluid occurs prior to or after treating at least aportion of the reaction product fluid derived from said hydroformylationprocess and which also contains phosphorus acidic compounds formedduring said hydroformylation process with water.
 17. The process ofclaim 1 wherein said metal-organophosphite ligand complex catalystcomprises rhodium complexed with an organophosphite ligand selectedfrom:(i) a monoorganophosphite represented by the formula: ##STR10##wherein R¹ represents a substituted or unsubstituted trivalenthydrocarbon radical containing from 4 to 40 carbon atoms or greater;(ii) a diorganophosphite represented by the formula: ##STR11## whereinR² represents a substituted or unsubstituted divalent hydrocarbonradical containing from 4 to 40 carbon atoms or greater and W representsa substituted or unsubstituted monovalent hydrocarbon radical containingfrom 1 to 18 carbon atoms or greater; (iii) a triorganophosphiterepresented by the formula: ##STR12## wherein each R⁶ is the same ordifferent and represents a substituted or unsubstituted monovalenthydrocarbon radical; and (iv) an organopolyphosphite containing two ormore tertiary (trivalent) phosphorus atoms represented by the formula:##STR13## wherein X represents a substituted or unsubstituted n-valenthydrocarbon bridging radical containing from 2 to 40 carbon atoms, eachR⁷ is the same or different and represents a divalent hydrocarbonradical containing from 4 to 40 carbon atoms, each R⁸ is the same ordifferent and represents a substituted or unsubstituted monovalenthydrocarbon radical containing from 1 to 24 carbon atoms, a and b can bethe same or different and each have a value of 0 to 6, with the provisothat the sum of a+b is 2 to 6 and n equals a+b.
 18. The process of claim1 wherein phosphorus acidic compounds present in the reaction productfluid are scavenged by an organic nitrogen compound that is also presentin said reaction product fluid and wherein at least some amount of thephosphorus acidic compound of the conversion products of the reactionbetween said phosphorus acidic compound and said organic nitrogencompound are also removed by the water treatment.
 19. The process ofclaim 18 wherein the organic nitrogen compound is selected from thegroup consisting of diazoles, triazoles, diazines and triazines.
 20. Theprocess of claim 19 wherein the organic nitrogen compound isbenzimidazole or benzotriazole.